Electrodepositable coating composition containing a cyclic guanidine

ABSTRACT

The present invention is directed towards an electrocoating composition comprising a cyclic guanidine.

CROSS-REFERENCE TO RELATED APPLICATION

This patent application is a Continuation of U.S. patent applicationSer. No. 11/835,600 filed on Aug. 8, 2007, the entirety of which isincorporated herein by reference.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention is directed towards an electrodepositable coatingcomposition comprising a cyclic guanidine.

2. Background Information

Dialkyltin oxides have traditionally been used as cure catalysts forelectrodeposition coatings. Dialkyltin oxides, however, have beensubjected to a number of regulatory restrictions by various countriesdue to environmental concerns. Therefore, bismuth has been used withincreased frequency as the cure catalyst for electrodeposition coatingsin lieu of dialkyltin oxide. There are, however, a number ofshortcomings associated with using bismuth as the cure catalyst. Forexample, bismuth is often a less effective catalyst for variouselectrodeposition compositions when compared to dialkyltin oxide.Moreover, there may be cost and availability issues associated withusing bismuth as a cure catalyst in the future. Accordingly, there is aneed for an alternative catalyst for use in an electrodepositioncoating. Moreover, there is also a need for an electrodeposition coatingthat is substantially free of tin.

SUMMARY OF THE INVENTION

The present invention is directed to an electrodepositable coatingcomposition comprising a cyclic guanidine.

DETAILED DESCRIPTION OF THE INVENTION

As used herein, unless otherwise expressly specified, all numbers suchas those expressing values, ranges, amounts or percentages may be readas if prefaced by the word “about”, even if the term does not expresslyappear. Moreover, it should be noted that plural terms and/or phrasesencompass their singular equivalents and vice versa. For example, “a”cyclic guanidine, “a” polymer, “a” crosslinker, and any other componentrefer to one or more of these components.

When referring to any numerical range of values, such ranges areunderstood to include each and every number and/or fraction between thestated range minimum and maximum.

As employed herein, the term “polyol” or variations thereof refersbroadly to a material having an average of two or more hydroxyl groupsper molecule.

As used herein, the term “polymer” refers broadly to prepolymers,oligomers and both homopolymers and copolymers. It should be noted thatthe prefix “poly” refers to two or more.

As stated above, the present invention is directed to anelectrodepositable coating composition comprising a cyclic guanidine. Itwill be understood that “guanidine” refers to a compound, moiety, and/orresidue having the following general structure:

wherein each of R1, R2, R3, R4, R5 (i.e., substituents of structure (I))can comprise hydrogen, (cyclo)alkyl, aryl, aromatic, organometallic, apolymeric structure, or together can form a cycloalkyl, aryl, or anaromatic structure, and wherein R1, R2, R3, R4, and R5 can be the sameor different. As used herein, “(cyclo)alkyl” refers to both alkyl andcycloalkyl. When any of the R groups “together can form a (clyco)alkyl,aryl, and/or aromatic group” it is meant that any two adjacent R groupsare connected to form a cyclic moiety, such as the rings in structures(II)-(V) below.

It will be appreciated that in some embodiments, the double bond betweenthe carbon atom and the nitrogen atom that is depicted in structure (I)may be located between the carbon atom and another nitrogen atom ofstructure (I). Accordingly, the various substituents of structure (I)may be attached to different nitrogens depending on where the doublebond is located within the structure.

In certain embodiments, the cyclic guanidine comprises the guanidine ofstructure (I) wherein two or more R groups of structure (I) togetherform one or more rings. In other words, in some embodiments the cyclicguanidine comprises ≧1 ring. For example, the cyclic guanidine caneither be a monocyclic guanidine (1 ring) as depicted in structures (II)and/or (III) below, or the cyclic guanidine can be polycyclic (≧2 rings)as depicted in structures (IV) and (V) below.

Each substituent of structures (II) and/or (III), R1-R7, can comprisehydrogen, (cyclo)alkyl, aryl, aromatic, organometallic, a polymericstructure, or together can form a cycloalkyl, aryl, or an aromaticstructure, and wherein R1-R7 can be the same or different. Similarly,each substituent of structures (IV) and (V), R1-R9, can be hydrogen,alkyl, aryl, aromatic, organometallic, a polymeric structure, ortogether can form a cycloalkyl, aryl, or an aromatic structure, andwherein R1-R9 can be the same or different. Moreover, in someembodiments of structures (II) and/or (III), certain combinations ofR1-R7 may be part of the same ring structure. For example, R1 and R7 ofstructure (II) may form part of a single ring structure. Moreover, insome embodiments, it will be understood that any combination ofsubstituents (R1-R7 of structures (II) and/or (III) as well as R1-R9 ofstructures (IV) and/or (V)) can be chosen so long as the substituents donot substantially interfere with the catalytic activity of the cyclicguanidine.

In certain embodiments, each ring in the cyclic guanidine is comprisedof ≧5-members. For instance, the cyclic guanidine may be a 5-memberring, a 6-member ring, or a 7-member ring. As used herein, the term“member” refers to an atom located in a ring structure. Accordingly, a5-member ring will have 5 atoms in the ring structure (“n” and/or “m”=1in structures (II)-(V)), a 6-member ring will have 6 atoms in the ringstructure (“n” and/or “m”=2 in structures (II)-(V)), and a 7-member ringwill have 7 atoms in the ring structure (“n” and/or “m”=3 in structures(II)-(V)). It will be appreciated that if the cyclic guanidine iscomprised of ≧2 rings (e.g., structures (IV) and (V)), the number ofmembers in each ring of the cyclic guanidine can either be the same ordifferent. For example, one ring may be a five-member ring while theother ring may be a six-member ring. If the cyclic guanidine iscomprised of ≧3 rings, then in addition to the combinations cited in thepreceding sentence, the number of members in a first ring of the cyclicguanidine can be different from the number of members in any other ringof the cyclic guanidine.

It will also be understood that in certain embodiments of the cyclicguanidine the nitrogen atoms of structures (II)-(V) can further haveadditional atoms attached thereto. Moreover, in some embodiments, thecyclic guanidine can either be substituted or unsubstituted. Forexample, as used herein in conjunction with the cyclic guanidine,“substituted”, in certain embodiments, refers to a cyclic guanidinewherein R5, R6, and/or R7 of structures (II) and/or (III) and/or R9 ofstructures (IV) and/or (V) is not hydrogen. As used herein inconjunction with the cyclic guanidine, “unsubstituted”, in certainembodiments, refers to a cyclic guanidine wherein R1-R7 of structures(II) and/or (III) and/or R1-R9 of structures (IV) and/or (V) ishydrogen. In some embodiments, the substituted cyclic guanidine is1,5,7-triazabicyclo [04.4.0]dec-5-ene.

It has been surprisingly discovered that the cyclic guanidine is itselfa catalyst (e.g., a curing catalyst) for the electrodepositable coatingcomposition. Accordingly, introduction of a cyclic guanidine into anelectrodepositable coating composition can reduce and/or eliminate theuse of metal catalysts, such as tin and/or bismuth, in anelectrodepositable coating composition.

In some embodiments, the cyclic guanidine of the present invention isused in combination with a metal, such as a metal ion, which can beadded to the electrodepositable coating composition. Metals that can beused in combination with the cyclic guanidine include, withoutlimitation, bismuth, tin, zinc, zirconium, titanium, manganese,tungsten, yttrium, molybdenum, lanthanum, cobalt, cerium, magnesium, orcombinations thereof. It is noted that the oxides and/or salts of themetals recited in the preceding sentence as well as an organofunctionalized material comprising one of the metals may also beutilized in the present invention. Moreover, it will be appreciated thatsome of the metal species are themselves catalysts and, therefore, actas a co-catalyst with the cyclic guanidine. Therefore, the amount ofmetal catalyst in an electrodepositable coating composition can bereduced by using the cyclic guanidine in combination with a metal.

In some embodiments, the electrodepositable coating compositioncomprises ≧0.01% or ≧0.2% by weight of the cyclic guanidine, based onthe total weight of the resin solids of the electrodepositable coatingcomposition. In other embodiments, the electrodepositable coatingcomposition comprises ≦7% or ≦4% or ≦2 by weight of the cyclicguanidine, based on the total weight of the resin solids of theelectrodepositable coating composition. In certain embodiments, theamount of cyclic guanidine present in the electrodepositable coatingcomposition can range between any combination of values, which wererecited in the preceding sentences, inclusive of the recited values. Forexample, in certain embodiments, the electrodepositable coatingcomposition comprises 0.6% to 2.0% by weight of the cyclic guanidine,based on the total weight of the resin solids of the electrodepositablecoating composition.

As will be discussed in greater detail below, the cyclic guanidine thatis described in the preceding paragraphs can be incorporated into theelectrodepositable coating composition using a variety of means. Forexample, the cyclic guanidine can be: (i) added as an additive to the anelectrodepositable coating composition; (ii) incorporated into the mainfilm-forming polymer of an electrodepositable coating composition; (iii)incorporated into the water dispersible polymer of a grind vehiclecomponent of an electrodepositable coating composition; (iv) used toblock a curing agent in an electrodepositable coating composition, (v)incorporated into a portion of a crater control additive, (vi)incorporated into a microgel, and/or (vii) used in any combinationthereof.

Electrodeposition baths are typically supplied as two components: (i) amain vehicle and (ii) a grind vehicle. The first component (mainvehicle) can be an unpigmented resin feed which generally comprises aresin blend. In certain embodiments, the resin blend comprises (a) amain film-forming polymer (e.g., an active hydrogen-containing ionicsalt group-containing resin) having reactive functional groups, (b) acuring agent that is reactive with functional groups on the film-formingpolymer, and (c) any additional water-dispersible non-pigmentedcomponents. Wide varieties of main film-forming polymers are known andcan be used in the electrodeposition baths of the invention so long asthe polymers are “water dispersible.” As used herein, “waterdispersible” will mean that a material is adapted to be solubilized,dispersed, and/or emulsified in water. The main film-forming polymersused in the invention are ionic in nature. Accordingly, in someembodiments, the main film-forming polymer is cationic. In other words,the main film-forming polymer comprises cationic salt groups, generallyprepared by neutralizing a functional group on the film-forming polymerwith an acid, which enables the main film-forming polymer to beelectrodeposited onto a cathode.

Examples of main film-forming polymers suitable for use in cationicelectrocoating coating compositions include, without limitation,cationic polymers derived from a polyepoxide, an acrylic, apolyurethane, and/or polyester, hydroxyl group-containing polymers,amine salt group-containing polymers, or combinations thereof. It shouldbe noted that in some embodiments, that main film-forming polymer is acopolymers of the polymers listed in the preceding sentence.

Accordingly, in some embodiments, the main film-forming polymer is acationic polymer (cationic resin) that is derived from a polyepoxide.For example, the main film-forming polymer can be prepared by reactingtogether a polyepoxide and a polyhydroxyl group-containing materialselected from alcoholic hydroxyl group-containing materials and phenolichydroxyl group-containing materials to chain extend or build themolecular weight of the polyepoxide. As will be discussed in greaterdetail below, the reaction product can then be reacted with a cationicsalt group former to produce the cationic polymer.

In certain embodiments, a chain extended polyepoxide typically isprepared as follows: the polyepoxide and polyhydroxyl group-containingmaterial are reacted together “neat” or in the presence of an inertorganic solvent such as a ketone, including methyl isobutyl ketone andmethyl amyl ketone, aromatics such as toluene and xylene, and glycolethers such as the dimethyl ether of diethylene glycol. The reactiontypically is conducted at a temperature of 80° C. to 160° C. for 30 to180 minutes until an epoxy group-containing resinous reaction product isobtained.

In some embodiments, the equivalent ratio of reactants (i.e.,epoxy:polyhydroxyl group-containing material) ranges from 1.00:0.50 to1.00:2.00.

In certain embodiments, the polyepoxide typically has at least two1,2-epoxy groups. The epoxy compounds may be saturated or unsaturated,cyclic or acyclic, aliphatic, alicyclic, aromatic or heterocyclic.Moreover, the epoxy compounds may contain substituents such as halogen,hydroxyl, and ether groups.

Examples of polyepoxides are those having a 1,2-epoxy equivalencygreater than one and/or two; that is, polyepoxides which have on averagetwo epoxide groups per molecule. Suitable polyepoxides includepolyglycidyl ethers of polyhydric alcohols such as cyclic polyols andpolyglycidyl ethers of polyhydric phenols such as Bisphenol A. Thesepolyepoxides can be produced by etherification of polyhydric phenolswith an epihalohydrin or dihalohydrin such as epichlorohydrin ordichlorohydrin in the presence of alkali. Besides polyhydric phenols,other cyclic polyols can be used in preparing the polyglycidyl ethers ofcyclic polyols. Examples of other cyclic polyols include alicyclicpolyols, particularly cycloaliphatic polyols such as hydrogenatedbisphenol A, 1,2-cyclohexane diol and 1,2-bis(hydroxymethyl)cyclohexane.

In certain embodiments, the polyepoxides have epoxide equivalent weights≧180. In some embodiments, the polyepoxides have epoxide equivalentweights ≦2000. In other embodiments, the polyepoxides have epoxideequivalent weights that range between any combination of values, whichwere recited in the preceding sentences, inclusive of the recitedvalues. For example, in certain embodiments the polyepoxides haveepoxide equivalent weights ranges from 186 to 1200.

Epoxy group-containing acrylic polymers may also be used in the presentinvention. In certain embodiments, epoxy group-containing acrylicpolymers have an epoxy equivalent weight ≧750. In other embodiments,epoxy group-containing acrylic polymer has an epoxy equivalent weight of≦2000. In some embodiments, the epoxy group-containing acrylic polymerhas an epoxy equivalent weight that ranges between any combination ofvalues, which were recited in the preceding sentences, inclusive of therecited values.

Examples of polyhydroxyl group-containing materials used to chain extendor increase the molecular weight of the polyepoxide (i.e., throughhydroxyl-epoxy reaction) include alcoholic hydroxyl group-containingmaterials and phenolic hydroxyl group-containing materials. Examples ofalcoholic hydroxyl group-containing materials are simple polyols such asneopentyl glycol; polyester polyols such as those described in U.S. Pat.No. 4,148,772; polyether polyols such as those described in U.S. Pat.No. 4,468,307; and urethane diols such as those described in U.S. Pat.No. 4,931,157. Examples of phenolic hydroxyl group-containing materialsare polyhydric phenols such as Bisphenol A, phloroglucinol, catechol,and resorcinol. Mixtures of alcoholic hydroxyl group-containingmaterials and phenolic hydroxyl group-containing materials may also beused.

The main film-forming polymer can contain cationic salt groups, whichcan be incorporated into the resin molecule as follows: The resinousreaction product prepared as described above is further reacted with acationic salt group former. By “cationic salt group former” is meant amaterial which is reactive with epoxy groups and which can be acidifiedbefore, during, or after reaction with the epoxy groups to form cationicsalt groups. Examples of suitable materials include amines such asprimary or secondary amines which can be acidified after reaction withthe epoxy groups to form amine salt groups, or tertiary amines which canbe acidified prior to reaction with the epoxy groups and which afterreaction with the epoxy groups form quaternary ammonium salt groups.Examples of other cationic salt group formers are sulfides which can bemixed with acid prior to reaction with the epoxy groups and form ternarysulfonium salt groups upon subsequent reaction with the epoxy groups.

When amines are used as the cationic salt formers, monoamines,hydroxyl-containing amines, polyamines, or combinations thereof may beused.

Tertiary and secondary amines are used more often than primary aminesbecause primary amines are polyfunctional with respect to epoxy groupsand have a greater tendency to gel the reaction mixture. If polyaminesor primary amines are used, they can be used in a substantialstoichiometric excess to the epoxy functionality in the polyepoxide soas to prevent gelation and the excess amine can be removed from thereaction mixture by vacuum stripping or other technique at the end ofthe reaction. The epoxy may be added to the amine to ensure excessamine.

Examples of hydroxyl-containing amines include, but are not limited to,alkanolamines, dialkanolamines, alkyl alkanolamines, and aralkylalkanolamines containing from 1 to 18 carbon atoms, such as 1 to 6carbon atoms, in each of the alkanol, alkyl and aryl groups. Specificexamples include ethanolamine, N-methylethanolamine, diethanolamine,N-phenylethanolamine, N,N-dimethylethanolamine, N-methyldiethanolamine,3-aminopropyldiethanolamine, and N-(2-hydroxyethyl)-piperazine.

Amines such as mono, di, and trialkylamines and mixed aryl-alkyl amineswhich do not contain hydroxyl groups or amines substituted with groupsother than hydroxyl which do not negatively affect the reaction betweenthe amine and the epoxy may also be used. Specific examples includeethylamine, methylethylamine, triethylamine, N-benzyldimethylamine,dicocoamine, 3-dimethylaminopropylamine, andN,N-dimethylcyclohexylamine.

Mixtures of the above mentioned amines may also be used in the presentinvention.

The reaction of a primary and/or secondary amine with the polyepoxidetakes place upon mixing of the amine and polyepoxide. The amine may beadded to the polyepoxide or vice versa. The reaction can be conductedneat or in the presence of a suitable solvent such as methyl isobutylketone, xylene, or 1-methoxy-2-propanol. The reaction is generallyexothermic and cooling may be desired. However, heating to a moderatetemperature ranging from 50° C. to 150° C. may be done to hasten thereaction.

The reaction product of the primary and/or secondary amine and thepolyepoxide is made cationic and water dispersible by at least partialneutralization with an acid. Suitable acids include organic andinorganic acids. Non-limiting examples of suitable organic acids includeformic acid, acetic acid, methanesulfonic acid, and lactic acid.Non-limiting examples of suitable inorganic acids include phosphoricacid and sulfamic acid. By “sulfamic acid” is meant sulfamic acid itselfor derivatives thereof such as those having the formula:

wherein R is hydrogen or an alkyl group having 1 to 4 carbon atoms.

It is noted that mixtures of the above mentioned acids may also be usedmay be used in the present invention.

The extent of neutralization of the cationic electrodepositable coatingcomposition varies with the particular reaction product involved.However, sufficient acid should be used to disperse theelectrodepositable coating composition in water. Typically, the amountof acid used provides at least 20 percent of all of the totalneutralization. Excess acid may also be used beyond the amount requiredfor 100 percent total neutralization. For example, in some embodiments,the amount of acid used to neutralize the electrodepositable coatingcomposition is ≧1% based on the total amines in the electrodepositablecoating composition. In other embodiments, the amount of acid used toneutralize the electrodepositable coating composition is ≦100% based onthe total amines in the electrodepositable coating composition. Incertain embodiments, the total amount of acid used to neutralize theelectrodepositable coating composition ranges between any combination ofvalues, which were recited in the preceding sentences, inclusive of therecited values. For example, the total amount of acid used to neutralizethe electrodepositable coating composition can be 20%, 35%, 50%, 60%, or80% based on the total amines in the electrodepositable coatingcomposition.

In the reaction of a tertiary amine with a polyepoxide, the tertiaryamine can be pre-reacted with the neutralizing acid to form the aminesalt and then the amine salt reacted with the polyepoxide to form aquaternary salt group-containing resin. The reaction is conducted bymixing the amine salt with the polyepoxide in water. Typically, thewater is present in an amount ranging from 1.75% to 20% by weight basedon total reaction mixture solids.

In forming the quaternary ammonium salt group-containing resin, thereaction temperature can be varied from the lowest temperature at whichthe reaction will proceed, generally room temperature or slightlythereabove, to a maximum temperature of 100° C. (at atmosphericpressure). At higher pressures, higher reaction temperatures may beused. In some embodiments, the reaction temperature ranges from 60° C.to 100° C. Solvents such as a sterically hindered ester, ether, orsterically hindered ketone may be used, but their use is not necessary.

In addition to the primary, secondary, and tertiary amines disclosedabove, a portion of the amine that is reacted with the polyepoxide canbe a ketimine of a polyamine, such as is described in U.S. Pat. No.4,104,147, column 6, line 23 to column 7, line 23. The ketimine groupsdecompose upon dispersing the amine-epoxy resin reaction product inwater. In an embodiment of the present invention, at least a portion ofthe active hydrogens present in the resin (a) comprise primary aminegroups derived from the reaction of a ketimine-containing compound andan epoxy group-containing material such as those described above.

In addition to resins containing amine salts and quaternary ammoniumsalt groups, cationic polymers containing ternary sulfonium groups maybe used in the composition of the present invention. Examples of theseresins and their method of preparation are described in U.S. Pat. Nos.3,793,278 and 3,959,106.

Suitable active hydrogen-containing, cationic salt group-containingresins can include copolymers of one or more alkyl esters of acrylicacid or (meth)acrylic acid optionally together with one or more otherpolymerizable ethylenically unsaturated monomers. Suitable alkyl estersof acrylic acid or (meth)acrylic acid include methyl (meth)acrylate,ethyl (meth)acrylate, butyl (meth)acrylate, ethyl acrylate, butylacrylate, and 2-ethyl hexyl acrylate. Suitable other copolymerizableethylenically unsaturated monomers include nitriles such acrylonitrileand (meth)acrylonitrile, vinyl and vinylidene halides such as vinylchloride and vinylidene fluoride and vinyl esters such as vinyl acetate.Acid and anhydride functional ethylenically unsaturated monomers such asacrylic acid, (meth)acrylic acid or anhydride, itaconic acid, maleicacid or anhydride, or fumaric acid may be used. Amide functionalmonomers including acrylamide, (meth)acrylamide, and N-alkyl substituted(meth)acrylamides are also suitable. Vinyl aromatic compounds such asstyrene and vinyl toluene can be used so long as a high level ofphotodegradation resistance of the polymer is not required.

Functional groups such as hydroxyl and amino groups can be incorporatedinto the acrylic polymer by using functional monomers such ashydroxyalkyl acrylates and methacrylates or aminoalkyl acrylates andmethacrylates. Epoxide functional groups (for conversion to cationicsalt groups) may be incorporated into the acrylic polymer by usingfunctional monomers such as glycidyl acrylate and methacrylate,3,4-epoxycyclohexylmethyl(meth)acrylate,2-(3,4-epoxycyclohexyl)ethyl(meth)acrylate, or allyl glycidyl ether.Alternatively, epoxide functional groups may be incorporated into theacrylic polymer by reacting carboxyl groups on the acrylic polymer withan epihalohydrin or dihalohydrin such as epichlorohydrin ordichlorohydrin.

The acrylic polymer can be prepared by traditional free radicalinitiated polymerization techniques, such as solution or emulsionpolymerization, as known in the art, using suitable catalysts whichinclude organic peroxides and azo type compounds and optionally chaintransfer agents such as alpha-methyl styrene dimer and tertiary dodecylmercaptan. Additional acrylic polymers which are suitable for formingthe active hydrogen-containing, cationic polymer and which can be usedin the electrodepositable coating compositions of the present inventioninclude those resins described in U.S. Pat. Nos. 3,455,806 and3,928,157.

As stated above, the main film-forming polymer can also be derived forma polyurethane. Among the polyurethanes which can be used are polymericpolyols which are prepared by reacting polyester polyols or acrylicpolyols such as those mentioned above with a polyisocyanate such thatthe OH/NCO equivalent ratio is greater than 1:1 so that free hydroxylgroups are present in the product. Smaller polyhydric alcohols such asthose disclosed above for use in the preparation of the polyester mayalso be used in place of or in combination with the polymeric polyols.

Additional examples of polyurethane polymers suitable for forming theactive hydrogen-containing, cationic polymer include the polyurethane,polyurea, and poly(urethane-urea) polymers prepared by reactingpolyether polyols and/or polyether polyamines with polyisocyanates. Suchpolyurethane polymers are described in U.S. Pat. No. 6,248,225.

Epoxide functional groups may be incorporated into the polyurethane bymethods well known in the art. For example, epoxide groups can beincorporated by reacting glycidol with free isocyanate groups.

Sulfonium group-containing polyurethanes can also be made by at leastpartial reaction of hydroxy-functional sulfide compounds, such asthiodiglycol and thiodipropanol, which results in incorporation ofsulfur into the backbone of the polymer. The sulfur-containing polymeris then reacted with a monofunctional epoxy compound in the presence ofacid to form the sulfonium group. Appropriate monofunctional epoxycompounds include ethylene oxide, propylene oxide, glycidol,phenylglycidyl ether, and CARDURA E, available from ResolutionPerformance Products.

In addition to being derived from a polyepoxide or a polyurethane, themain film-forming polymer can also be derived from a polyester. Suchpolyesters can be prepared in a known manner by condensation ofpolyhydric alcohols and polycarboxylic acids. Suitable polyhydricalcohols include, for example, ethylene glycol, propylene glycol,butylene glycol, 1,6-hexylene glycol, neopentyl glycol, diethyleneglycol, glycerol, trimethylol propane, and pentaerythritol. Examples ofsuitable polycarboxylic acids used to prepare the polyester includesuccinic acid, adipic acid, azelaic acid, sebacic acid, maleic acid,fumaric acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalicacid, and trimellitic acid. Besides the polycarboxylic acids mentionedabove, functional equivalents of the acids such as anhydrides where theyexist or lower alkyl esters of the acids such as the methyl esters maybe used. Moreover, hydroxy acids and/or lactones, such as caprolactoneand/or 12-hydroxystearic acid, may also be used as components of thepolyester.

The polyesters contain a portion of free hydroxyl groups (resulting fromthe use of excess polyhydric alcohol and/or higher polyols duringpreparation of the polyester) which are available for cure reactions.

Epoxide functional groups may be incorporated into the polyester byreacting carboxyl groups on the polyester with an epihalohydrin ordihalohydrin such as epichlorohydrin or dichlorohydrin. Alternatively,in some embodiments, an acid functional polyester can be incorporatedinto an epoxy polymer by reaction of carboxyl groups with an excess ofpolyepoxide.

Sulfonium salt groups can be introduced by the reaction of an epoxygroup-containing polymer of the types described above with a sulfide inthe presence of an acid, as described in U.S. Pat. Nos. 3,959,106 and4,715,898. Sulfonium groups can be introduced onto the polyesterbackbones described using similar reaction conditions.

In some embodiments, the main film-forming polymer further comprisescationic amine salt groups which are derived from pendant and/orterminal amino groups. By “terminal and/or pendant” is meant thatprimary and/or secondary amino groups are present as a substituent whichis pendant from or in the terminal position of the polymeric backbone,or, alternatively, is an end-group substituent of a group which ispendant and/or terminal from the polymer backbone. In other words, theamino groups from which the cationic amine salt groups are derived arenot required to be within the polymeric backbone. The pendant and/orterminal amino groups can have the following structures (I) or (II):

wherein R represents H or C₁ to C₁₈ alkyl; R¹, R², R³, and R⁴ are thesame or different, and each independently represents H or C₁ to C₄alkyl; and X and Y can be the same or different, and each independentlyrepresents a hydroxyl group and/or an amino group.

As used in conjunction with structures (V) and (VI), “alkyl” is meantalkyl and aralkyl, cyclic or acyclic, linear or branched monovalenthydrocarbon groups. The alkyl groups can be unsubstituted or substitutedwith one or more heteroatoms, for example, non-carbon, non-hydrogenatoms such as one or more oxygen, nitrogen or sulfur atoms.

The pendant and/or terminal amino groups represented by structures (V)and (VI) above can be derived from a compound selected from the groupconsisting of ammonia, methylamine, diethanolamine, diisopropanolamine,N-hydroxyethyl ethylenediamine, diethylenetriamine, and mixturesthereof. One or more of these compounds is reacted with one or more ofthe above described polymers, for example, a polyepoxide polymer, wherethe epoxy groups are ring-opened via reaction with a polyamine, therebyproviding terminal amino groups and secondary hydroxyl groups.

In some embodiments, the terminal amino groups has structure (VI)wherein both X and Y comprise primary amino groups (e.g., the aminogroup is derived from diethylenetriamine). It should be understood thatin this instance, prior to reaction with the polymer, the primary aminogroups can be blocked, for example, by reaction with a ketone such asmethyl isobutyl ketone, to form the diketimine. Such ketimines are thosedescribed in U.S. Pat. No. 4,104,147, column 6, line 23 to column 7,line 23. The ketimine groups can decompose upon dispersing theamine-epoxy reaction product in water, thereby providing free primaryamine groups as curing reaction sites.

In certain embodiments, the amines from which the pendant and/orterminal amino groups are derived comprise primary and/or secondaryamine groups such that the active hydrogens of said amines will beconsumed by reaction with the at least partially blocked aliphaticpolyisocyanate curing agent to form urea groups or linkages during thecuring reaction.

It should be understood that, in some embodiments, the active hydrogensassociated with the main film-forming polymer include any activehydrogens which are reactive with isocyanates at temperatures sufficientto cure the electrodepositable coating composition as previouslydiscussed (i.e., at temperatures at or below 182.2° C. (360° F.)). Theactive hydrogens typically are derived from reactive hydroxyl groups,and primary and secondary amino, including mixed groups such as hydroxyland primary amino. In some embodiments of the present invention, atleast a portion of the active hydrogens are derived from hydroxyl groupscomprising phenolic hydroxyl groups. In some embodiments, the mainfilm-forming polymer has an active hydrogen content of ≧1milliequivalents of active hydrogen per gram of resin solids. In otherembodiments, the main film-forming polymer has an active hydrogencontent of ≦4 milliequivalents of active hydrogen per gram of resinsolids. In certain embodiments, the main film-forming polymer has anactive hydrogen content ranging between any combination of values, whichwere recited in the preceding sentences, inclusive of the recitedvalues. For example, in some embodiments, the main film-forming polymerhas an active hydrogen content ranging from 2 to 3 milliequivalents ofactive hydrogen per gram of resin solids.

The extent of cationic salt group formation should be such that when theresin is mixed with an aqueous medium and other ingredients, a stabledispersion of the electrodepositable coating composition will form. By“stable dispersion” is meant one that does not settle or is easilyredispersible if some settling occurs. Moreover, the dispersion shouldbe of sufficient cationic character that the dispersed resin particleswill electrodeposite on a cathode when an electrical potential is set upbetween an anode and a cathode immersed in the aqueous dispersion.

In certain embodiments, the main film-forming polymer in theelectrodepositable coating composition of the present inventioncomprises ≧0.1 milliequivalents of cationic salt group per gram of resinsolids. In other embodiments, the main film-forming polymer comprises≦3.0 milliequivalents of cationic salt group per gram of resin solids.In some embodiments, the milliequivalents of cationic salt group pergram of resin solids in the main film-forming polymer ranges between anycombination of values, which were recited in the preceding sentences,inclusive of the recited values. For example, in some embodiments, theelectrodepositable coating composition comprises from 0.1 to 0.7milliequivalents of cationic salt group per gram of resin solids.

Moreover, in some embodiments, the main film-forming polymer typicallyis non-gelled, having a number average molecular weight ≧2000. In otherembodiments, the main film-forming polymer is non-gelled and has anumber average molecular weight of ≦15,000. In certain embodiments, theaverage molecular weight of the main film-forming polymer ranges betweenany combination of values, which were recited in the precedingsentences, inclusive of the recited values. For example, in someembodiments, the average molecular weight of the main film-formingpolymer ranges from 5000 to 10,000. As used herein, “non-gelled” means apolymer that is substantially free from crosslinking, and prior tocationic salt group formation, the resin has a measurable intrinsicviscosity when dissolved in a suitable solvent. In contrast, a gelledresin, having an essentially infinite molecular weight, would have anintrinsic viscosity too high to measure.

In certain embodiments, the main film-forming polymer is present in theelectrodepositable coating composition in an amount≧40% by weight basedon weight of total resin solids present in the electrodepositablecoating composition. In other embodiments, the main film-forming polymeris present the electrodepositable coating composition in an amount≦95%by weight based on weight of total resin solids present in theelectrodepositable coating composition. In some embodiments, the weightpercent of the main film-forming polymer in the electrodepositablecoating composition ranges between any combination of values, which wererecited in the preceding sentences, inclusive of the recited values. Forexample, the main film-forming polymer is present in theelectrodepositable coating composition in an amount ranging from 50% to75% by weight based on weight of total resin solids present in theelectrodepositable coating composition.

In some embodiments, the main film-forming polymers can be selected fromcationic acrylic polymers such as those described in U.S. Pat. Nos.3,455,806 and 3,928,157. In some embodiments, the main film-formingpolymer can be selected from the polymers described in U.S. Pat. Nos.6,165,338 and 4,543,376, which are incorporated herein by reference. Incertain embodiments, the main film-forming polymers can be selected fromhydroxy group-containing polymers including, without limitation, thereaction products of: (i) bisphenol A and ethylene oxide, (ii) bisphenolA and propylene oxide, (iii) bisphenol A and polyethylene oxide and/orpolypropylene oxide diamines, and/or (iv) bisphenol A and bisphenol Adiglycidyl ether. In other embodiments, the main film-forming polymerscan be amine salt group-containing polymers including, withoutlimitation, the acid-solubilized reaction products of polyepoxides andprimary or secondary amines such as those described in U.S. Pat. Nos.3,663,389; 3,984,299; 3,947,338; 3,947,339; and 4,116,900. Suitableprimary or secondary amines include, without limitation, methyl ethanolamine, diethanolamine, diethylene triamine diketimine, diethyl amine,dimethyl amine, other di alkyl amines, amino propyl diethanols amine, orcombinations thereof. Usually, these amine salt group-containingpolymers are used in combination with a blocked isocyanate curing agent.The isocyanate can be fully blocked as described in the aforementionedU.S. Pat. No. 3,984,299 or the isocyanate can be partially blocked andreacted with the polymer backbone such as described in U.S. Pat. No.3,947,338. Also, one-component compositions as described in U.S. Pat.No. 4,134,866 and DE-OS No. 2,707,405 can be used as the film-formingresin.

Besides amine salt group-containing polymers, quaternary ammonium saltgroup-containing polymers can also be employed. Examples of thesepolymers are those which are formed by reacting an organic polyepoxidewith a tertiary amine salt. Such polymers are described in U.S. Pat.Nos. 3,962,165; 3,975,346; and 4,001,101. Examples of other cationicpolymers are ternary sulfonium salt group-containing polymers andquaternary phosphonium salt-group containing polymers such as thosedescribed in U.S. Pat. Nos. 3,793,278 and 3,984,922, respectively. Also,film-forming polymers which cure via transesterification such asdescribed in European Application No. 12463 can be used. Further,cationic compositions prepared from Mannich bases such as described inU.S. Pat. No. 4,134,932 can be used.

As stated above, in addition to the (a) main film-forming polymer, theresin blend further comprises (b) a curing agent (crosslinker) that isreactive with reactive functional groups, such as active hydrogengroups, on the main film-forming polymer. The curing agents that may beused with the present invention include, but is not limited to,urethane, isocyanate, ester, or combinations thereof.

It will be understood that non-limiting examples of urethane curingagents include the products of (i) an amine-carbonate reaction and/or(ii) an isocyanate-alcohol reaction.

Non-limiting examples of suitable cyclic carbonates that can be utilizedto form the urethane curing agent, include, without limitation,propylene carbonate, ethylene carbonate, butylene carbonate, orcombinations thereof. Non-limiting examples of suitable acycliccarbonates that can be utilized to form the urethane, include, withoutlimitation, dimethyl carbonate, diethyl carbonate, methylethylcarbonate, dipropyl carbonate, methylpropyl carbonate, dibutylcarbonate, or combinations thereof. In some embodiments of the presentinvention, the acyclic carbonate comprises dimethyl carbonate.Non-limiting examples of suitable amines that can be utilized to formthe urethane, include, without limitation, diethylene triamine,dipropylene triamine, bis-hexamethylene triamine, isophorone diamine,4′-bis-aminocyclohexylamine, xylylene diamine, N-hydroxyethyl ethylenediamine, hexamethylene triamine, trisaminoethylamine, or combinationsthereof. In some embodiments, the curing agent is a reaction product ofa polyamine and a cyclic carbonate. It will be understood that incertain embodiments, the primary amines of the polyamine are reactedwith the cyclic carbonate. In some embodiments of the present invention,the reaction product of the polyamine and the cyclic carbonate can thenbe reacted with an epoxy functional polymer such as those used toprepare the main vehicle and/or grind vehicle. Specifically, in someembodiments, the secondary amine of the reaction product is reacted withthe epoxy functional group of the epoxy functional polymer.

Non-limiting examples of suitable isocyanates that can be utilized toform the urethane curing agent include, without limitation, toluenediisocyanate, methylene diphenyl 4,4′-diisocyanate, isophoronediisocyanate, hexamethylene diisocyanate, xylyleuediisocyanate,tetramethylxylylene diisocyanate, straight chain aliphatic diisocyanatessuch as 1,4-tetramethylene diisocyanate, norbornane diisocyanate, and1,6-hexamethylene diisocyanate, isophorone diisocyanate and4,4′-methylene-bis-(cyclohexyl isocyanate), aromatic diisocyanates suchas p-phenylene diisocyanate, diphenylmethane-4,4′-diisocyanate and 2,4-or 2,6-toluene diisocyanate, higher polyisocyanates such astriphenylmethane-4,4′,4″-triisocyanate, 1,2,4-benzene triisocyanate andpolymethylene polyphenyl isocyanate, and trimers of 1,6-hexamethylenediisocyanate, or combinations thereof. It should be noted that thedimers, trimers and higher functional materials of these isocyanates mayalso be utilized in the present invention. Non-limiting examples ofsuitable alcohols that can be utilized to form the urethane include,without limitation, methanol, ethanol, propanol, isopropanol, butanol,glycol ethers, and other alcohols.

As stated above, suitable curing agents for amine salt group-containingpolymers, cationic acrylic polymers, and/or hydroxy group-containingpolymers include isocyanates as well as blocked isocyanates. It shouldbe noted that as used herein, “isocyanates” also includespolyisocyanates and vice versa. The polyisocyanate curing agent may be afully blocked polyisocyanate with substantially no free isocyanategroups, or it may be partially blocked and reacted with the resinbackbone as described in U.S. Pat. No. 3,984,299. The polyisocyanate canbe an aliphatic, an aromatic polyisocyanate, or combinations thereof. Insome embodiments, diisocyanates are utilized, although in otherembodiments higher polyisocyanates can be used in place of or incombination with diisocyanates.

Isocyanate prepolymers, for example, reaction products ofpolyisocyanates with polyols such as neopentyl glycol and trimethylolpropane or with polymeric polyols such as polycaprolactone diols andtriols (NCO/OH equivalent ratio greater than one) can also be used. Amixture of diphenylmethane-4,4′-diisocyanate and polymethylenepolyphenyl isocyanate can be used.

Any suitable alcohol or polyol can be used as a blocking agent for thepolyisocyanate in the electrodepositable coating composition of thepresent invention provided that the agent will deblock at the curingtemperature and provided a gelled product is not formed. For example,suitable alcohols include, without limitation, methanol, ethanol,propanol, isopropyl alcohol, butanol, 2-ethylhexanol, butoxyethanol,hexyloxyethanol, 2-ethylhexyloxyethanol, n-butanol, cyclohexanol phenylcarbinol, methylphenyl carbinol, ethylene glycol monobutyl ether,diethylene glycol monobutylether, ethylene glycol monomethylether,propylene glycol monomethylether, or combinations thereof.

In certain embodiments of the present invention, the blocking agentcomprises one or more 1,3-glycols and/or 1,2-glycols. In one embodimentof the present invention, the blocking agent comprises one or more1,2-glycols, typically one or more C₃ to C₆,2-glycols. For example, theblocking agent can be selected from at least one of 1,2-propanediol,1,3-butanediol, 1,2-butanediol, 1,2-pentanediol, timethylpentene diol,and/or 1,2-hexanediol.

Other suitable blocking agents include oximes such as methyl ethylketoxime, acetone oxime and cyclohexanone oxime and lactams such asepsilon-caprolactam.

As stated above, in some embodiments, the curing agent that is used inthe present invention is an ester curing agent. It should be noted thatas used herein, “ester” also includes polyesters. Accordingly, in someembodiments, a polyester curing agent. Suitable polyester curing agentsinclude materials having greater than one ester group per molecule. Theester groups are present in an amount sufficient to effectcross-linking, for example at temperatures up to 250° C., and curingtimes of up to 90 minutes. It should be understood that acceptable curetemperatures and cure times will be dependent upon the substrates to becoated and their end uses.

Compounds generally suitable as the polyester curing agent arepolyesters of polycarboxylic acids. Non-limiting examples includebis(2-hydroxyalkyl)esters of dicarboxylic acids, such asbis(2-hydroxybutyl) azelate and bis(2-hydroxyethyl)terephthalate;tri(2-ethylhexanoyl)trimellitate; and poly(2-hydroxyalkyl)esters ofacidic half-esters prepared from a dicarboxylic acid anhydride and analcohol, including polyhydric alcohols. The latter type is suitable toprovide a polyester with a final functionality of more than 2. Onesuitable example includes a polyester prepared by first reactingequivalent amounts of the dicarboxylic acid anhydride (e.g., succinicanhydride or phthalic anhydride) with a trihydric or tetrahydricalcohol, such as glycerol, trimethylolpropane or pentaerythritol, attemperatures below 150° C., and then reacting the acidic polyester withat least an equivalent amount of an epoxy alkane, such as 1,2-epoxybutane, ethylene oxide, or propylene oxide. The polyester curing agent(ii) can comprise an anhydride. Another suitable polyester comprises alower 2-hydroxy-alkylterminated poly-alkyleneglycol terephthalate.

In some embodiments, the polyester comprises at least one ester groupper molecule in which the carbon atom adjacent to the esterifiedhydroxyl has a free hydroxyl group.

Also suitable is the tetrafunctional polyester prepared from thehalf-ester intermediate prepared by reacting trimellitic anhydride andpropylene glycol (molar ratio 2:1), then reacting the intermediate with1,2-epoxy butane and the glycidyl ester of branched monocarboxylicacids.

In some embodiments, where the active hydrogen-containing resincomprises cationic salt groups, the polyester curing agent issubstantially free of acid. For purposes of the present invention, by“substantially free of acid” is meant having less than 0.2 meq/g acid.For aqueous systems, for example for cathodic electrocoating, coatingcompositions, suitable polyester curing agents can include non-acidicpolyesters prepared from a polycarboxylic acid anhydride, one or moreglycols, alcohols, glycol mono-ethers, polyols, and/or monoepoxides.

Suitable polycarboxylic anhydrides can include dicarboxylic acidanhydrides, such as succinic anhydride, phthalic anhydride,tetrahydrophthalic anhydride, trimellitic anhydride, hexahydrophthalicanhydride, methylhexahydrophthalic anhydride,3,3′,4,4′-benzophenonetetracarboxylic dianhydride, and pyromelliticdianhydride. Mixtures of anhydrides can be used.

Suitable alcohols can include linear, cyclic or branched alcohols. Thealcohols may be aliphatic, aromatic or araliphatic in nature. As usedherein, the terms glycols and mono-epoxides are intended to includecompounds containing not more than two alcohol groups per molecule whichcan be reacted with carboxylic acid or anhydride functions below thetemperature of 150° C.

Suitable mono-epoxides can include glycidyl esters of branchedmonocarboxylic acids. Further, alkylene oxides, such as ethylene oxideor propylene oxide may be used. Suitable glycols can include, forexample ethylene glycol and polyethylene glycols, propylene glycol andpolypropylene glycols, and 1,6-hexanediol. Mixtures of glycols may beused.

Non-acidic polyesters can be prepared, for example, by reacting, in oneor more steps, trimellitic anhydride (TMA) with glycidyl esters ofbranched monocarboxylic acids in a molar ratio of 1:1.5 to 1:3, ifdesired with the aid of an esterification catalyst such as stannousoctoate or benzyl dimethyl amine, at temperatures of 50-150° C.Additionally, trimellitic anhydride can be reacted with 3 molarequivalents of a monoalcohol such as 2-ethylhexanol.

Alternatively, trimellitic anhydride (1 mol) can be reacted first with aglycol or a glycol monoalkyl ether, such as ethylene glycol monobutylether in a molar ratio of 1:0.5 to 1:1, after which the product isallowed to react with 2 moles of glycidyl esters of branchedmonocarboxylic acids. Furthermore, the polycarboxylic acid anhydridei.e., those containing two or three carboxyl functions per molecule) ora mixture of polycarboxylic acid anhydrides can be reactedsimultaneously with a glycol, such as 1,6-hexane diol and/or glycolmono-ether and monoepoxide, after which the product can be reacted withmono-epoxides, if desired. For aqueous compositions these non-acidpolyesters can also be modified with polyamines such as diethylenetriamine to form amide polyesters. Such “amine-modified” polyesters maybe incorporated in the linear or branched amine adducts described aboveto form self-curing amine adduct esters.

The non-acidic polyesters of the types described above typically aresoluble in organic solvents, and typically can be mixed readily with themain film forming resin described above.

Polyesters suitable for use in an aqueous system or mixtures of suchmaterials disperse in water typically in the presence of resinscomprising cationic salt groups.

In some embodiments, the polyisocyanate curing agents are typicallyutilized in conjunction with the cationic main film-forming polymers inamounts of ≧5% by weight based on the total weight of the resin solidsof the electrodeposition bath. In other embodiments, the polyisocyanatecuring agents are typically utilized in conjunction with the cationicmain film-forming polymers in amounts of ≦60% by weight based on thetotal weight of the resin solids of the electrodeposition bath. In yetother embodiments, the amount of main film-forming polymer can rangebetween any combination of values, which were recited in the precedingsentences, inclusive of the recited values. For example, thepolyisocyanate curing agents can be utilized in conjunction with thecationic main film-forming polymers in an amount ranting from 20% to 50%by weight based on the total weight of the resin solids of theelectrodeposition bath.

In some embodiments, the curing agent that can be used in theelectrocoating composition is the curing agent that is described in U.S.Pat. No. 5,902,473, which is incorporated herein by reference.

It is understood that one skilled in the art can determine anappropriate curing agent for a particular main film-forming polymerbased on the functionality of the main film-forming polymer.

In certain embodiments, at least a portion of the curing agent ischemically bound to the main film-forming polymer. In other embodiments,the curing agent is not chemically bound to the main film-formingpolymer and is added as an additive to the electrodepositable coatingcomposition.

The second component (grind vehicle) of an electrodeposition bathgenerally comprises a pigment composition (pigment paste), which canhave one or more pigments, a water dispersible polymer, and, optionally,additives such as surfactants, wetting agents, catalysts, dispersingaids, or combinations thereof. It should be noted that the waterdispersible polymer of the grind vehicle can either be the same ordifferent from the main film-forming polymer in the resin blend. Thepigment composition used in the grind vehicle may be of the conventionaltype comprising pigments of, for example, iron oxides, strontiumchromate, carbon black, coal dust, titanium dioxide, talc, bariumsulfate, as well as color pigments such as cadmium yellow, cadmium red,chromium yellow and the like. In some embodiments, the pigmentcomposition can comprise effect pigments such as, but not limited to,electroconductive and/or photo chromic pigments. The pigment content ofthe dispersion is usually expressed as a pigment-to-resin ratio. In thepractice of the invention, when pigment is employed, thepigment-to-resin ratio is usually within the range of about 0.02:1 to1:1. The other additives mentioned above are usually in the dispersionin amounts of about 0.01% to 3% by weight based on weight of resinsolids.

The first and second components of the electrodeposition bath aredispersed together in an aqueous medium which comprises water and,usually, coalescing solvents to form the electrodeposition bath. Usefulcoalescing solvents that can be used in the electrodeposition bathinclude, but are not limited to, hydrocarbons, alcohols, esters, ethersand/or ketones. In one embodiment, the coalescing solvents includealcohols, polyols and ketones. Specific coalescing solvents includeisopropanol, butanol, 2-ethylhexanol, isophorone, 2-methoxypentanone,ethylene and propylene glycol and the monoethyl, monobutyl and monohexylethers of ethylene glycol. In certain embodiments, the amount ofcoalescing solvent used in the electrodeposition bath is ≧0.01% weightbased on the total weight of the aqueous medium used to make theelectrodeposition bath. In other embodiments, the amount of coalescingsolvent used in the electrodeposition bath is ≦25% by weight based onthe total weight of the aqueous medium used to make theelectrodeposition bath. In yet other embodiments, the amount ofcoalescing solvent used in the electrodeposition bath can range betweenany combination of values, which were recited in the precedingsentences, inclusive of the recited values. For example, in oneembodiment, the amount of coalescing solvent used in theelectrodeposition bath can range from 0.05% to 5% by weight based on thetotal weight of the aqueous medium used to make the electrodepositionbath.

As stated above, in certain embodiments, the cyclic guanidine can be inthe form of an additive that is added to an electrodepositable coatingcomposition. In some embodiments, the additive is added “neat”, that is,added directly into the electrodepositable coating composition withoutprior blending or reacting with the other components that comprise theelectrodepositable coating composition. For example, in someembodiments, the additive is added “neat” into an electrodeposition bathand/or to components that are used to form the electrodeposition bath(e.g., resin blend and/or grind vehicle). In other embodiments, theadditive is added to an aqueous medium prior to the aqueous medium beingadded to the electrodeposition bath. For instance, the additive can beadded to an aqueous medium, which is added to the electrodepositionbath, after the electrodeposition bath has been prepared (i.e., postadded). In some embodiments, the additive is added “neat” into the resinblend and/or into the grind vehicle before the resin blend and/or thegrind vehicle is dispersed in an aqueous medium. In other words, theadditive can be added to the resin blend and/or to the grind vehicleprior to the formation of the electrodeposition bath. The preparation ofsuch an additive will be discussed in greater detail in the Examplessection below.

In certain embodiments, additive that is added to the electrodepositablecoating composition comprises a reaction product of the cyclic guanidineand a monofunctional compound. Suitable monofunctional compoundsinclude, without limitation,

Moreover, in some embodiments, the cyclic guanidine of the presentinvention is incorporated into the resin blend and/or the grind vehicleas part of an admixture that comprises the cyclic guanidine and anadditional component. It will be appreciated that the cyclic guanidineas well as the additional component are both reactive with a functionalgroup on the main film-forming polymer and/or the water dispersiblepolymer of the resin blend and/or grind vehicle, respectively. In someembodiments, the additional component is an “amine package” that isadded to the resin blend and/or the grind vehicle. As used herein,“amine package” refers to an admixture of amines, such as, withoutlimitation, polyamines, primary amines, secondary amines,amine-carbamates, tertiary amines, or combinations thereof.

In other embodiments, the additional component can include a sulfide ora combination of an amine package and a sulfide. Suitable sulfides thatcan be utilized in the present invention include, but are not limitedto, hydroxy functional sulfides, such as thiodiethanol.

In certain embodiments, the additional component comprises otherfunctional groups such as, without limitation, alcohols, tertiaryamines, urethanes, ureas, ketimines, carbamates, or combinationsthereof.

In some embodiments, the carbamate functional group is a reactionproduct of a polyamine and a carbonate, such as a cyclic carbonate.Suitable polyamines that can be utilized to form the carbamate include,without limitation, diethylene triamine, dipropylene triamine,bis-hexamethylene triamine, isophorone diamine,4′-bis-aminocyclohexylamine, xylylene diamine, N-hydroxyethyl ethylenediamine, hexamethylene triamine, trisaminoethylamine, or combinationsthereof. In certain embodiments, the polyamine comprises primary and/orsecondary amines. Suitable carbonates that can be utilized to form thecarbamate include, without limitation, ethylene carbonate, propylenecarbonate, butylene carbonate, or mixtures thereof.

In some embodiments, the additional component comprises a reactionproduct of a polyamine and a carbonate. The polyamines and carbonateswhich are listed in the preceding paragraph are suitable for use informing such a reaction product. In certain embodiments, the polyaminecomprises a primary amine and a secondary amine. In some embodiments, atleast a portion of the primary amine of the polyamine is reacted with acyclic carbonate to form a carbamate.

In some embodiments, the cyclic guanidine is the only component of theadmixture that reacts with the polymer of the resin blend and/or thegrind vehicle.

As stated above, in certain embodiments, the cyclic guanidine can beincorporated into a polymer, such as the main film-forming polymerand/or the water dispersible polymer of the grind vehicle, of anelectrodepositable coating composition. For clarity, the mainfilm-forming polymer and the water dispersible polymer of the grindvehicle will generally be referred to as a “polymer.” For example, thecyclic guanidine can be incorporated into a polymer via a reactionbetween the cyclic guanidine and a functional group on the polymer. Insome embodiments, the cyclic guanidine is incorporated into an epoxyfunctional polymer by reacting with an epoxy functional group on thepolymer. The preparation of a polymer incorporating the cyclic guanidinewill be discussed in greater detail in the Examples section below.

In some embodiments of the present invention, the polymeric reactionproduct of the cyclic guanidine and a polymer may be rendered cationicand water dispersible by a variety of methods. For example, in someembodiments, the reaction product of a polymer and the cyclic guanidineis rendered cationic and water dispersible by neutralizing at least aportion of the cyclic guanidine moieties that are bonded to the polymerwith an acid such as lactic acid, acetic acid, sulfamic formic acid,phosphoric acid, methanesulfonic acid, para toluenesulfonic acid,dimethylolpropionic acid, other acids, or combinations thereof. In someembodiments, the polymer is rendered cationic and water dispersible byneutralizing at least a portion of the amines that are bonded to thepolymer with an acid (i.e., the cyclic guanidines are not neutralized).In yet other embodiments, the polymer is rendered cationic and waterdispersible by neutralizing at least a portion of the cyclic guanidinesand at least a portion of the amines, each of which are bonded to thepolymer, with an acid.

As stated above, in certain embodiments of the invention, the curingagent that is utilized in the electrodepositable coating compositioncomprises the reaction product of the cyclic guanidine and anisocyanate. In some embodiments, isocyanate comprises aliphaticisocyanate, an aromatic isocyanate, or combinations thereof. Onepotential advantage of these embodiments is that the incorporation ofthe cyclic guanidine into the curing agent creates a blocked curingcatalyst. In other words, upon the application of heat to the curingagent, the cyclic guanidine is released from the curing agent and isutilized to catalyze the curing process of the electrodepositablecoating composition.

Moreover, in some embodiments, the cyclic guanidine is used to block atleast a portion of the curing agent. Accordingly, it will be understoodthat once the curing agent is de-blocked (i.e., the cyclic guanidine isno longer blocking the curing agent), the curing agent is able to reactwith functional groups on the main film-forming polymer thereby curingthe main film-forming polymer while the cyclic guanidine catalyzes thecuring process.

As stated above, in certain embodiments, a crater control additive,which can incorporated into the electrodepositable coating composition,can comprise the cyclic guanidine. Suitable crater control additivesinclude, without limitation, those described in U.S. Pat. Nos.4,420,574, 4,423,166, and 4,423,850, which are incorporated herein byreference. For example, in some embodiments, the cyclic guanidine can beused in lieu of at least a portion of the amines that are utilized toform a the crater control additive.

As stated above, in some embodiments, a microgel, which can beincorporated into the electrodepositable coating composition, cancomprise the cyclic guanidine. A suitable microgel that can be utilizedis described in U.S. Pat. No. 5,096,556, which is incorporated herein byreference. For example, in certain embodiments, the cyclic guanidine canbe used in lieu of at least a portion of the amines that are utilized toform the microgel.

The electrodepositable coating composition of the present invention canbe applied onto a number of substrates. Accordingly, the presentinvention is further directed to a substrate that is coated, at least inpart, with the electrodepositable coating composition described herein.It will be understood that the electrocoating coating composition can beapplied onto a substrate as a monocoat or as a coating layer in amulti-layer coating composite. Non-limiting examples of a suitablesubstrate can include a metal, a metal alloy, and/or a substrate thathas been metallized such as nickel plated plastic. For example, themetal or metal alloy can include aluminum and/or steel. In oneembodiment, the steel could be cold rolled steel, electrogalvanizedsteel, and hot dipped galvanized steel. In one embodiment, at least aportion of the surface of the metallic surface onto which the coating isapplied is pretreated with phosphate, such as zinc phosphate. In certainembodiments, the coated substrate may comprise a portion of a vehiclesuch as a vehicular body (e.g., without limitation, door, body panel,trunk deck lid, roof panel, hood, and/or roof) and/or a vehicular frame.As used herein, the term “vehicle” or variations thereof includes, butis not limited, to civilian, commercial, and military land vehicles suchas cars and trucks.

Moreover, the electrodepositable coating composition of the presentinvention may be applied onto the substrate to impart a wide variety ofproperties such as, but not limited to, corrosion resistance, chipresistance, filling (i.e., ability to hide underlying substrateroughness), abrasion resistance, impact damage, flame and/or heatresistance, chemical resistance, UV light resistance, and/or structuralintegrity.

Depending on the substrate, the electrodepositable coating compositionis applied (i.e., electrodeposited) onto a substrate using a voltagethat can range from 1 volt to several thousand volts. In one embodiment,the voltage that is used ranges from 50 volts to 500 volts. Moreover, inone embodiment, the current density is usually between 0.5 ampere and 5amperes per square foot. It will be understood, however, that thecurrent density tends to decrease during electrodeposition which is anindication of the formation of an insulating film.

After the coating has been applied onto the substrate viaelectrodeposition, in one embodiment, the coating is cured by baking thesubstrate at an elevated temperature ranging from 90° C. to 260° C. fora time period ranging from 1 minute to 40 minutes.

As stated above, in certain embodiments, the electrodepositable coatingcomposition of the present invention is utilized in an electrocoatinglayer that is part of a multi-layer coating composite comprising asubstrate with various coating layers. The coating layers could includea pretreatment layer, such as a phosphate layer (e.g., zinc phosphatelayer), an electrocoating layer which results form theelectrodepositable coating composition of the present invention, andsuitable top coat layers (e.g., base coat, clear coat layer, pigmentedmonocoat, and color-plus-clear composite compositions). It is understoodthat suitable topcoat layers include any of those known in the art, andeach independently may be waterborne, solventborne, in solid particulateform (i.e., a powder coating composition), or in the form of a powderslurry. The top coat typically includes a film-forming polymer,crosslinking material and, if a colored base coat or monocoat, one ormore pigments. In one embodiment, the primer layer is disposed betweenthe electrocoating layer and the base coat layer. In certainembodiments, one or more of the topcoat layers are applied onto asubstantially uncured underlying layer. For example, in someembodiments, a clear coat layer is applied onto at least a portion of asubstantially uncured basecoat layer (wet-on-wet), and both layers aresimultaneously cured in a downstream process.

Moreover, in some embodiments, the top coat layers may be applieddirectly onto the electrodepositable coating layer. In other words, insome embodiments, the substrate lacks a primer layer. For example, insome embodiments, a basecoat layer is applied directly onto at least aportion of the electrodepositable coating layer.

It will also be understood that in certain embodiments, the top coatlayers may be applied onto an underlying layer despite the fact that theunderlying layer has not been fully cured. For example, a clearcoatlayer may be applied onto a basecoat layer even though the basecoatlayer has not been subjected to a curing step. Both layers can then becured during a subsequent curing step thereby eliminating the need tocure the basecoat layer and the clearcoat layer separately.

In certain embodiments, additional ingredients such as colorants andfillers can be present in the various coating compositions from whichthe top coat layers result. Any suitable colorants and fillers may beused. For example, the colorant can be added to the coating in anysuitable form, such as discrete particles, dispersions, solutions and/orflakes. A single colorant or a mixture of two or more colorants can beused in the coatings of the present invention. It should be noted that,in general, the colorant can be present in a layer of the multi-layercomposite in any amount sufficient to impart the desired property,visual and/or color effect.

Example colorants include pigments, dyes and tints, such as those usedin the paint industry and/or listed in the Dry Color ManufacturersAssociation (DCMA), as well as special effect compositions. A colorantmay include, for example, a finely divided solid powder that isinsoluble but wettable under the conditions of use. A colorant can beorganic or inorganic and can be agglomerated or non-agglomerated.Colorants can be incorporated into the coatings by grinding or simplemixing. Colorants can be incorporated by grinding into the coating byuse of a grind vehicle, such as an acrylic grind vehicle, the use ofwhich will be familiar to one skilled in the art.

Example pigments and/or pigment compositions include, but are notlimited to, carbazole dioxazine crude pigment, azo, monoazo, disazo,naphthol AS, salt type (lakes), benzimidazolone, condensation, metalcomplex, isoindolinone, isoindoline and polycyclic phthalocyanine,quinacridone, perylene, perinone, diketopyrrolo pyrrole, thioindigo,anthraquinone, indanthrone, anthrapyrimidine, flavanthrone, pyranthrone,anthanthrone, dioxazine, triarylcarbonium, quinophthalone pigments,diketo pyrrolo pyrrole red (“DPP red BO”), titanium dioxide, carbonblack, zinc oxide, antimony oxide, etc. and organic or inorganic UVopacifying pigments such as iron oxide, transparent red or yellow ironoxide, phthalocyanine blue and mixtures thereof. The terms “pigment” and“colored filler” can be used interchangeably.

Example dyes include, but are not limited to, those that are solventand/or aqueous based such as acid dyes, azoic dyes, basic dyes, directdyes, disperse dyes, reactive dyes, solvent dyes, sulfur dyes, mordantdyes, for example, bismuth vanadate, anthraquinone, perylene, aluminum,quinacridone, thiazole, thiazine, azo, indigoid, nitro, nitroso,oxazine, phthalocyanine, quinoline, stilbene, and triphenyl methane.

Example tints include, but are not limited to, pigments dispersed inwater-based or water miscible carriers such as AQUA-CHEM 896commercially available from Degussa, Inc., CHARISMA COLORANTS andMAXITONER INDUSTRIAL COLORANTS commercially available from AccurateDispersions division of Eastman Chemical, Inc.

As noted above, the colorant can be in the form of a dispersionincluding, but not limited to, a nanoparticle dispersion. Nanoparticledispersions can include one or more highly dispersed nanoparticlecolorants and/or colorant particles that produce a desired visible colorand/or opacity and/or visual effect. Nanoparticle dispersions caninclude colorants such as pigments or dyes having a particle size ofless than 150 nm, such as less than 70 nm, or less than 30 nm.Nanoparticles can be produced by milling stock organic or inorganicpigments with grinding media having a particle size of less than 0.5 mm.Example nanoparticle dispersions and methods for making them areidentified in U.S. Pat. No. 6,875,800 B2, which is incorporated hereinby reference. Nanoparticle dispersions can also be produced bycrystallization, precipitation, gas phase condensation, and chemicalattrition (i.e., partial dissolution). In order to minimizere-agglomeration of nanoparticles within the coating, a dispersion ofresin-coated nanoparticles can be used. As used herein, a “dispersion ofresin-coated nanoparticles” refers to a continuous phase in which isdispersed discreet “composite microparticles” that comprise ananoparticle and a resin coating on the nanoparticle. Exampledispersions of resin-coated nanoparticles and methods for making themare identified in U.S. application Ser. No. 10/876,031 filed Jun. 24,2004, which is incorporated herein by reference, and U.S. ProvisionalApplication No. 60/482,167 filed Jun. 24, 2003, which is alsoincorporated herein by reference.

In some embodiments, special effect compositions that may be used in oneor more layers of the multi-layer coating composite include pigmentsand/or compositions that produce one or more appearance effects such asreflectance, pearlescence, metallic sheen, phosphorescence,fluorescence, photochromism, photosensitivity, thermochromism,goniochromism and/or color-change. Additional special effectcompositions can provide other perceptible properties, such asreflectivity, opacity or texture. In a non-limiting embodiment, specialeffect compositions can produce a color shift, such that the color ofthe coating changes when the coating is viewed at different angles.Example color effect compositions are identified in U.S. Pat. No.6,894,086, incorporated herein by reference. Additional color effectcompositions can include transparent coated mica and/or synthetic mica,coated silica, coated alumina, a transparent liquid crystal pigment, aliquid crystal coating, and/or any composition wherein interferenceresults from a refractive index differential within the material and notbecause of the refractive index differential between the surface of thematerial and the air.

In other embodiments, a photosensitive composition and/or photochromiccomposition, which reversibly alters its color when exposed to one ormore light sources, can be used in a number of layers in the multi-layercomposite. Photochromic and/or photosensitive compositions can beactivated by exposure to radiation of a specified wavelength. When thecomposition becomes excited, the molecular structure is changed and thealtered structure exhibits a new color that is different from theoriginal color of the composition. When the exposure to radiation isremoved, the photochromic and/or photosensitive composition can returnto a state of rest, in which the original color of the compositionreturns. In one non-limiting embodiment, the photochromic and/orphotosensitive composition can be colorless in a non-excited state andexhibit a color in an excited state. Full color-change can appear withinmilliseconds to several minutes, such as from 20 seconds to 60 seconds.Example photochromic and/or photosensitive compositions includephotochromic dyes.

In certain embodiments, the photosensitive composition and/orphotochromic composition can be associated with and/or at leastpartially bound to, such as by covalent bonding, a polymer and/orpolymeric materials of a polymerizable component. In contrast to somecoatings in which the photosensitive composition may migrate out of thecoating and crystallize into the substrate, the photosensitivecomposition and/or photochromic composition associated with and/or atleast partially bound to a polymer and/or polymerizable component inaccordance with a non-limiting embodiment of the present invention, haveminimal migration out of the coating. Example photosensitivecompositions and/or photochromic compositions and methods for makingthem are identified in U.S. application Ser. No. 10/892,919 filed Jul.16, 2004 and incorporated herein by reference.

While specific embodiments of the invention have been described indetail, it will be appreciated by those skilled in the art that variousmodifications and alternatives to those details could be developed inlight of the overall teachings of the disclosure. Accordingly, theparticular arrangements disclosed are meant to be illustrative only andnot limiting as to the scope of the invention which is to be given thefull breadth of the claims appended and any and all equivalents thereof.

Examples Example 1 (a) An Undispersed Electrodepositable Resin

A EPON 880¹ 1103.88 Bisphenol A 402.83 Methyl isobutyl ketone 168.60 BEthyltriphenyl phosphonium iodide 1.45 C Crosslinker² 961.62 D Diethanolamine 18.94 E Diketimine³ 97.64 F Butylcarbitol formal 294.91 Methylisobutyl ketone 92.34 G Epoxy additive⁴ 790.10 ¹Epoxy resin availablefrom Hexion Specialty Chemicals ²Crosslinker prepared from the reactionof Hexamethylene triamine and propylene carbonate in 70% solids in MIBK³MIBK diketimine of diethylene triamine at 72.7% in MIBK ⁴Epoxy additivewas prepared by reacting EPON 880 with BPA to EEW of 935 and aminatingwith diethanol amine and ketimine.

Procedure: All weights are in grams. Items A and B are charged to a 4neck round bottom flask, fit with a stirrer, temperature measuringprobe, N₂ blanket and heated to 130° C. The mixture exotherms. Begin 1hour hold at 145° C. The peak exotherm was 146° C. and the temperatureallowed to drop to 145° C. After 1 hour, the reaction was cooled to 110°C. and charge C, D and E were added. The mixture was held at 115° C. fortwo hours. Charge F then was added and the mixture held for 30 minutes.Charge G then was added and the mixture held for an additional 30minutes.

Example 2 (a) A Crosslinker

# Material gm 1 Isocyanate¹ 1876.00 2 Dibutyltin dilaurate 0.35 3 Methylisobutyl ketone (mibk) 21.73 4 Diethyleneglycol monobutyl ether 454.24 5Ethyleneglycol monobutyl ether 1323.62 6 Methylisobutyl ketone (mibk)296.01 ¹Rubinate M, available from Huntsman Corporation

Procedure: All weights are in grams. Items 1, 2 and 3 are charged to a 4neck round bottom flask, fit with a stirrer, temperature measuring probeand N₂ blanket. Charge 4 was added slowly allowing the temperature toincrease to 60° C. The mixture was then held at 60° C. for 30 minutes.Charge 5 was then added over about 2 hours allowing the temperature toincrease to a maximum of 110° C. Charge 6 was then added and the mixturewas held at 110° C. until the i.r. spectrum indicates no residualisocyanate.

Example 3 (a) A Cationic Resin

# Material Gm 1 EPON 828¹ 614.68 2 Bisphenol A 265.42 3 MACOL 98 A MOD1² 125.0 4 Methylisobutyl ketone (mibk) 31.09 5 Ethyltriphenylphosphonium iodide 0.60 6 MACOL 98 A MOD 1² 125.00 7 Methylisobutylketone (mibk) 52.05 8 Example 2, crosslinker 719.67 9 Ketimine³ 57.01 10N-methyl ethanolamine 48.68 11 sulfamic acid 19.36 12 H2O 573.84 13 H2O657.65 14 H2O 550.0 ¹Epoxy resin available from Hexion SpecialtyChemicals. ²Bisphenol ethylene oxide adduct available from BASFCorporation. ³MIBK diketimine of diethylene triamine at 72.7% in MIBK.

Procedure: All weights are in grams. Items 1, 2, 3, 4 and 5 are chargedto a 4 neck round bottom flask, fit with a stirrer, temperaturemeasuring probe, N₂ blanket and heated to 130° C. The mixture exothermsto about 150° C. The temperature was allowed to drop to 145° C. and heldat this temperature for 2 hours. Charges 6 and 7 were then added.Charges 8, 9 and 10 were added and the mixture was held at 122° C. fortwo hours. 877g of the reaction mixture was poured into a solution ofitems 11 and 12 with good stirring. The resulting dispersion was mixedfor thirty minutes and then charge 13 was added with stirring over about30 minutes and mixed well. Charge 14 was added and mixed well. About 600g of water and solvent are distilled off under vacuum at 60-65° C. Theresulting aqueous dispersion had a solids content of 38.80%.

Example 4 (a) An Additive

# Description Weight (gm) 1 1,5,7-triazabicyclo(4.4.0)dec-5-ene 50.00 2Toluene 150.00 3 2-ethyl hexyl glycidyl ether 79.2

Procedure: All weights are in grams. Items 1, and 2 are charged, underN₂, to a round bottom flask fitted with a mechanical stirrer, condenser,and temperature controlling probe. The mixture was heated to 60° C. Item3 was added drop-wise over 30 minutes. The mixture was then brought toreflux and held at reflux for an hour. The toluene was then removed byfirst using ordinary distillation, followed by vacuum distillation at60° C. Final product was, by theory, 100% nonvolatile.

Example 5 (a) A Blocked Isocyanate

# Material Weight 1 Rubinate M¹ 402.00 2 Dibutyltin dilaurate 0.08 3Mibk 45.00 4 Diethyleneglycol monobutyl ether 97.34 5 Ethylene glycolmonobutyl ether 207.41 6 1,5,7-triazabicyclo(4.4.0)dec-5-ene 81.01 7Mibk 23.42 TOTAL 856.26 ¹Polymeric isocyanate available from HuntsmanCorp.

Procedure: All weights are in grams. Items 1, 2 and 3 are charged to a 4neck round bottom flask, fit with a stirrer, temperature measuring probeand N₂ blanket. Charge 4 was added slowly allowing the temperature toincrease to 60° C. The mixture was then held at 60° C. for 30 minutes.Charge 5 was then added over about 1 hour allowing the temperature toincrease to a maximum of 110° C. The mixture was held for 30 minutes at110° C. Charge 6 was then added and the mixture was held at 110° C.until the i.r. spectrum indicates no residual isocyanate. Heating wasstopped; charge 7 was added and mixed well. The final product wastitrated with 0.2 N HCl and found to contain 0.736 meq. base per gram ofresin.

Example 6 (a) Cure Results Set 1

In the following cure examples, resins were made undispersed in solvent,blended with crosslinker (Cure example A and B) and catalyst, stirreduntil uniform, and allowed to set overnight. The coatings were thenapplied using a Bird Bar applicator to approximately 25 micron filmthickness. The panels were then allowed to flash at room temperature forat least 1 hr, then cured in an electric oven at the temperature andtime indicated. The panels were tested for cure by acetone double rubsusing ASTM D5402-6 Method A with the following exceptions: Acetone wasused rather than MIBK, no water cleaning of panel, 100 double rubs aredone using a cheese cloth, and the rating scale was as listed below.

1 through to substrate in <50 2 Through in 50-100 rubs 3 Very severelymarred. Scratches to metal easily 4 Severely marred only over arearubbed. Can Scratch to metal 5 Marred over rub area, can scratch throughto metal 6 Marred uniformly in center of rub area, difficult, butpossible to scratch to metal 7 Non uniform marring over rub area, cannot scratch to metal 8 Scratching, very little marring of rub area, cannot scratch to metal 9 Slight scratching of rub area, can not scratch tometal 10 No visible damage

Solvent Resistance Acetone Acetone Cure Catalyst DR DR Example MainVehicle Crosslinker % R.S. 160 C./30′ 177CF/30′ A Resin as in Example 3,Polymeric MDI, 10 Dibutyl tin 100-no — but undispersed, and equivalents(functionality dilaurate, effect without crosslinker 2.7) reacted with 20.76% Sn on Rating = (item 8 in the equivalents of ethylene resin solids10 synthesis) and without glycol butyl ether, and 8 any acid or waterequivalents of diethylene (items 11 through 14). glycol butyl ether. Theresin was diluted Blended with MV to form to 65% solids with 35%crosslinker on resin propylene glycol solids. The blocked methyl ether,then urethane crosslinkers were 1.6% water was added. used at 65% solidsin MIBK. B Resin as in Example 3, Polymeric MDI, 10 BCG-2EHGE 100-no —but undispersed, and equivalents (functionality (Additive effect withoutcrosslinker 2.7) reacted with 2 from Rating = (item 8 in the equivalentsof ethylene Example 2), 10 synthesis) and without glycol butyl ether,and 8 0.75% BCG any acid or water equivalents of diethylene on totalresin (items 11 through 14). glycol butyl ether. solids The resin wasdiluted Blended with MV to form to 65% solids with 35% crosslinker onresin propylene glycol solids. The blocked methyl ether, then urethanecrosslinkers were 1.6% water was added. used at 65% solids in MIBK. CResin as in Example 3, Polymeric MDI reacted 0.75% BCG 100- 100-no butundispersed, and with Diethyleneglycol on resin scratch effect withoutcrosslinker monobutyl ether solids from Rating = 8 Rating = (item 8 inthe Ethylene glycol crosslinker 10 synthesis) and without monobutylether any acid or water 1,5,7- (items 11 through 14).triazabicyclo(4.4.0)dec-5- The resin was diluted ene (BCG). Blended withto 65% solids with MV to form 35% propylene glycol crosslinker on resinsolids. methyl ether, then The blocked urethane 1.6% water was added.crosslinkers were used at 65% solids in MIBK. D Resin as in Example 3,Polymeric MDI, 10 BCG-2EHGE 100-no 100-no but undispersed, andequivalents (functionality (Additive effect effect without crosslinker2.7) reacted with 10 from Rating = Rating = (item 8 in the equivalentsof Example 2), 10 10 synthesis) and without caprolactam. Blended 0.75%BCG any acid or water with MV to form 35% on total resin (items 11through 14. crosslinker on resin solids. solids The resin was diluted to65% solids with propylene glycol methyl ether, then 1.6% water wasadded. E** Resin as in Example 3, Poly functional blocked BCG reacted100-no 100-no but undispersed, and urethane made from 24.6 into resn,effect effect without crosslinker parts ketoxime, 12.6 parts 0.75% onRating = Rating = (item 8 in the TMP, 62.7 parts IPDI. total resin 10 10synthesis) and without Blended with MV to form solids any acid or water35% crosslinker on resin (items 11 through 14). solids. Additionally,enough of the n methyl ethanol amine was replaced with BCG to provide0.75% BCG on total resin solids. The resin was diluted to 65% solidswith propylene glycol methyl ether, then 1.6% water was added. FUndispersed resin Aliphatic carbamate Dibutyl tin 100-no synthesized asin integral in resin dilaurate effect example 1 with 0.76% Sn on Rating= integral carbamate resin solids 10 crosslinker, 71% solids in MIBKsolvent with 1.2% water added to resin solution G Undispersed resinAliphatic carbamate BCG-2EHGE 100-no synthesized as in integral in resin(Additive effect example 1 with from Rating = integral carbamate Example4), 10 crosslinker, 71% 0.75% BCG solids in MIBK on total resin solventwith 1.2% solids. water added to resin solution H Undispersed resinAliphatic carbamate BCG-2EHGE 100-no synthesized as in integral in resin(Additive effect example 1 with from Rating = integral carbamate Example4), 10 crosslinker, 71% 1.5% BCG solids in MIBK on total resin solventwith 1.2% solids. water added to resin solution BCG =,5,7-triazabicyclo(4.4.0)dec-5-ene **Also 100 ADR no effect cured at 135C. 30′

Example 7 (a) A Cationic Resin

# Material Parts 1 EPON 828¹ 1023 2 Bisphenol A-ethylene oxide adduct365 3 Bisphenol A 297 4 2-Butoxyethanol 187.2 5 Benzyldimethylamine 1.46 Benzyldimethylamine 3.0 7 Diketimine¹ 182.3 8 N-methylethanolamine85.2 9 Sulfamic acid 171.1 10 Deionized water 1065.9 11 Deionized water735.9 12 Deionized water 1156.4 13 Deionized water 867.3 ¹See Example 1

Materials #1-4 (EPON 828, bisphenol A-ethylene oxide adduct, bisphenol Aand 2-butoxyethanol) were charged into a reaction vessel and heatedunder a nitrogen atmosphere to 125° C. The first portion of thebenzyldimethylamine, Material #5, was added and the reaction allowed toexotherm to around 180° C. When the reaction reached 160° C., a one hourhold was started. After the peak exotherm the resin was allowed to coolback to 160° C., continuing the hold. After the hold the reaction wasthen cooled to 130° C. and the second portion of benzyldimethylamineMaterial #6, was added. The reaction was held at 130° C. until anextrapolated epoxy equivalent weight of 1070. At the expected epoxyequivalent weight materials 7 and 8 (Diketimine andN-methylethanolamine) were added in succession and the mixture allowedto exotherm to around 150° C. At the peak exotherm a one hour hold wasstarted while allowing the reaction to cool to 125° C. After the onehour hold the resin was dispersed in an aqueous medium consisting ofsulfamic acid and the first portion of deionized water. The dispersionwas later reduced with the second, third, and fourth portions ofdeionized water. The resulting cationic soap was vacuum striped untilthe methyl isobutyl ketone liberated by the hydrolysis of the diketimewas less than 0.05%.

To 2517g of the above aqueous polymer solution was added 443g deionizedwater. The mixture was heated to 70° C. under a nitrogen blanket. 66.4 gof an 85% solution of EPON 828 in mibk was then added over 15 minuteswith good agitation. 5.81 g of mibk was added as a rinse for the EPON828 solution and the mixture held at 70° C. for 45 minutes. The mixturewas heated to 90° C. over 70 minutes and held at this temperature for 3hours with good mixing. 337g of deionized water was then added and thedispersion cooled to less than 35° C. and poured out.

Example 8 (a) A Cationic Resin

# Material Parts 1 EPON 828 752 2 bisphenol a 228 3 Butyl carbitolformal 108.89 4 etppi 0.752 5 Butyl carbitol formal 298.63 6 JEFFAMINEd2000 2687.74 7 sulfamic acid 131.93 8 H2O 7812.62

Materials 1, 2, 3 are added to a suitably equipped round bottom flask.The mixture was then heated to 125° C. Material 4 was then added. Thereaction mixture was allowed to exotherm to 160° C., add heat asrequired to reach 160° C. The reaction mixture was then held at 160-170°C. for 1 hr. Material 5 was added and mixed well. Material 6 was thenadded as rapidly as possible. The resulting reaction mixture was heatedto 130° C., and held for 3 hrs. Materials 7, and 8 are preblended andthe reaction mixture was added to the acidic water solution underagitation to form a cationic dispersion.

Example 9 (a) A Cationic Resin

# Material gm 1 EPON 828¹ 307.34 2 Bisphenol A 132.71 3 MACOL 98 A MOD1² 62.50 4 Methylisobutyl ketone (mibk) 15.54 5 Ethyltriphenylphosphonium iodide 0.30 6 MACOL 98 A MOD 1² 62.50 7 Methylisobutylketone (mibk) 34.30 8 Ketimine³ 28.50 9 N-methyl ethanolamine 7.80 101,5,7-triazabicyclo(4.4.0)dec-5-ene 30.66 11 Example 2, crosslinker458.05 12 sulfamic acid 23.17 13 H2O 568.1 14 H2O 780.2 15 H2O 550.0¹Epoxy resin available from Hexion Specialty Chemicals ²Bisphenolethylene oxide adduct available from BASF Corporation. ³MIBK diketimineof diethylene triamine at 72.7% in MIBK

Procedure: All weights are in grams. Items 1, 2, 3, 4 and 5 are chargedto a 4 neck round bottom flask, fit with a stirrer, temperaturemeasuring probe, N₂ blanket and heated to 130° C. The mixture exothermsto about 150° C. The temperature was allowed to drop to 145° C. and heldat this temperature for 2 hours. Charges 6 and 7 were then added.Charges 8, 9 and 10 were added and the mixture was held at 122° C. fortwo hours. Charge 11 (preheated to ˜60° C.) was added and mixed for 10minutes without heat. 969g of the reaction mixture was poured into asolution of items 12 and 13 with good stirring. The resulting dispersionwas mixed for thirty minutes and then charge 14 was added with stirringover about 30 minutes and mixed well. Charge 15 was added and mixedwell. About 600 g of water and solvent are distilled off under vacuum at60-65° C. The resulting aqueous dispersion had a solids content of34.16%.

Example 10 (a) A Cationic Resin

# Material gm 1 EPON 828¹ 614.68 2 Bisphenol A 265.42 3 MACOL 98 A MOD1² 125.0 4 Methylisobutyl ketone (mibk) 31.09 5 Ethyltriphenylphosphonium iodide 0.60 6 MACOL 98 A MOD 1² 125.00 7 Methylisobutylketone (mibk) 50.10 8 Example 2, crosslinker 894.95 9 Ketimine³ 57.01 10N-methyl ethanolamine 48.68 11 sulfamic acid 40.52 12 H2O 1196.9 13 Gumrosin solution⁴ 17.92 14 H2O 1623.3 15 H2O 1100.0 ¹Epoxy resin availablefrom Hexion Specialty Chemicals. ²Bisphenol ethylene oxide adductavailable from BASF Corporation. ³MIBK diketimine of diethylene triamineat 72.7% in MIBK. ⁴30% by weight solution of gum rosin in diethyleneglycol mono butyl ether formal.

Procedure: All weights are in grams. Items 1, 2, 3, 4 and 5 are chargedto a 4 neck round bottom flask, fit with a stirrer, temperaturemeasuring probe, N₂ blanket and heated to 130° C. The mixture exothermsto about 150° C. The temperature was allowed to drop to 145° C. and heldat this temperature for 2 hours. Charges 6 and 7 were then added.Charges 8, 9 and 10 were added and the mixture was held at 122° C. fortwo hours. 1991g of the reaction mixture was poured into a solution ofitems 11 and 12 with good stirring. Charge 13 was then added and theresulting dispersion was mixed for thirty minutes and then charge 14 wasadded with stirring over about 30 minutes and mixed well. Charge 15 wasadded and mixed well. About 1100 g of water and solvent are distilledoff under vacuum at 60-65° C. The resulting aqueous dispersion had asolids content of 39.37%.

Example 11 (a) A Cationic resin

# Material gm 1 DER 732¹ 711 2 Bisphenol A 164.5 3 benzyldimethyl amine1.65 4 butyl Carbitol formal² 78.8 5 JEFFAMINE D400³ 184.7 6 bisphenol Adiglycidyl ether⁴ 19.1 7 butyl Carbitol formal 3.4 Resin from reactionproduct of materials 1-7 988.6 8 Deionized water 1242.13 9 Sulfamic acid30.2 10 Deionized water 614.8 ¹Aliphatic epoxy resin available from DowChemical Co. ²Available as MAZON 1651 from BASF Corporation³Polyoxypropylene diamine available from Huntsman Corp. ⁴Available fromHexion Corporation as EPON 828

Materials 1 and 2 are charged into a suitably equipped 3-literround-bottomed flask. The mixture was heated to 130° C. and Material 3was added. The reaction mixture was held at 135° C. until the epoxideequivalent weight of the mixture was 1232. Material 4 was then added andthen the mixture was cooled to 95° C. Material 5 was added and thereaction held at 95° C. until the Gardner-Holdt viscosity of a sample ofthe resin diluted 50/50 in methoxy propanol is “H-J”. A mixture ofmaterials 6 and 7 were added and the mixture held until theGardner-Holdt viscosity of a sample of the resin diluted 50/50 inmethoxy propanol was “Q−”. 988.6 g of this resin was poured into amixture of 1242.13 g deionized water and 30.2 g sulfamic and mixed for30 minutes. 614.8 g deionized water was then added and mixed well. Thefinal aqueous dispersion had a measured solids content of 35.8%

Example 12 (a) A Pigment Paste

# Material Parts 1 Cationic Resin Example 11 1793 2 SURFYNOL GA¹ 5.28 3TiO₂ ² 157.54 4 Kaolin Clay³ 1235.82 5 Carbon Black⁴ 16.94 6 Deionizedwater 41.36 ¹A Surfactant available from Air Products Inc. ²CR800Eavailable from Kerr McGee ³ASP-200 available from BASF Corporation.⁴CSX-333 carbon black available from Cabots Inc.

Materials 1 and 2 were preblended in a flat bottom metal container.Materials 3 through 5 were added sequentially to the mixture under ahigh shear cowles. The paste was cowles for 30 min. Material 6 was addedunder low shear mixing and the paste was stirred until uniform. Thepaste was then transferred to a RED HEAD medial mill equipped with awater cooling jacket and using 2 mm zircoa media. The paste was thenmilled until a Hegman of ≧7 was observed.

Example 13 (a) A Paint

# Material Parts 1 Example 8, Cationic resin 113.73 2 Butyl carbitolFormal¹ 4.61 3 Example 7, Cationic resin 40.98 4 Example 9 Cationicresin 504.52 5 Example 10 Cationic resin 369.37 6 Ethylene Glycol hexylether 10.36 7 Deionized water 24 8 Example 12, Pigment Paste 129.26 9Deionized water 1789.32 ¹Available as MAZON 1651 from BASF Corporation

Materials 1-9 are added sequentially under agitation and stirred untiluniform to create the resin blend. This results in a paint with 1.28% onRS of 1,5,7-triazabicyclo(4.4.0)dec-5-ene coming from the resin. Twentypercent by weight of the paint was removed by ultrafiltration andreplaced by deionized water.

Example 14 (a) A Paint

# Material Parts 1 Cationic resin Example 8 754.12 2 Butyl carbitolFormal¹ 40.39 3 Cationic resin Example 7 359.10 4 Cationic resin²6556.21 5 Ethylene Glycol hexyl ether 90.86 6 Deionized water 214 7Example 12, Pigment Paste 1357.80 8 Dibutyl tin oxide paste³ 147.63 9Deionized water 9472.05 ¹Available as MAZON 1651 from BASF Corporation.²Similar to Example 3, but with the addition of 0.5% gum rosin on resinsolids, total solids of 42.8% ³A cationic dibutyl tin oxide pasteconsisting of a sulfonium epoxy grind vehicle and dibutyl tin oxide,total solids of 55.7 in water, dibutyl tin oxide weight percent was36.63.

Materials 1-9 are added sequentially under agitation and stirred untiluniform to create the resin blend. This results in a paint with 1.3% onRS of dibutyl tin oxide catalyst and was used as a control reference.Twenty percent by weight of the paint was removed by ultrafiltration andreplaced by deionized water.

Example 15 (a) A Grind Vehicle

# Material gm 1 EPON 828¹ 533.2 2 nonyl phenol 19.1 3 bisphenol A 198.34 ethyltriphenyl phosphonium iodide 0.7 5 butoxy propanol 201.6 6methoxy propanol 50.4 7 1,5,7-triazabicyclo(4.4.0)dec-5-ene ¹Epoxy resinavailable from Hexion Specialty Chemicals

Procedure: All weights are in grams. Items 1, 2, 3, 4 and 5 are chargedto a 4 neck round bottom flask, fit with a stirrer, temperaturemeasuring probe, N₂ blanket and heated to 130° C. The mixture exothermsto 160-180° C. Hold at 160-170° C. for 1 hour. Turn heat off and add 6slowly. At 60° C. add 7. Allow the mixture to exotherm to 110° C. thenhold at 110-120° C. for 1 hour. To 920 g of the reaction mixture, add39g sulfamic acid and 1153 g deionized water and mix well. Add anadditional 15.6 g sulfamic acid and mix well. The mixture was a viscousslightly hazy solution with a solids content of 38.2%.

Example 16 (a) Grind Vehicle pH Adjustment

1 Example 15, Grind Vehicle 809.9 2 10% sulfamic acid solution 49.26

Materials were added sequentially resulting in a resin dispersion withpH of 7.05.

(b) A Pigment Paste

# Material Parts 1 pH adjusted GV from above 595.44 2 SURFYNOL GA¹ 1.453 TiO₂ ² 43.14 4 Kaolin Clay³ 338.63 5 Carbon Black⁴ 4.64 6 Deionizedwater 46.7 ¹A Surfactant available from Air Products Inc. ²CR800Eavailable from Kerr McGee ³ASP-200 available from BASF Corporation.⁴CSX-333 carbon black available from Cabots Inc.

Materials 1 and 2 were preblended in a flat bottom metal container.Materials 3 through 5 were added sequentially to the mixture under ahigh shear cowles. The paste was cowlesed for 30 min. Material 6 wasadded under low shear mixing and the paste was stirred until uniform.The paste was then transferred to a RED HEAD medial mill equipped with awater cooling jacket and using 2 mm zircoa media. The paste was thenmilled until a Hegman of >7 was observed.

Example 17 (a) A Paint

# Material Parts 1 Cationic resin, Example 8 191.1 2 Butyl carbitolFormal¹ 7.73 3 Cationic resin, Example 7 68.76 4 Example 3 Cationicresin (at 38.1% NV) 1400.34 5 Ethylene Glycol hexyl ether 17.4 6 PigmentPaste, Example 16 256.43 7 Deionized water 1871.7 ¹Available as MAZON1651 from BASF Corporation

Materials 1-7 are added sequentially under agitation and stirred untiluniform to create the resin blend. This results in a paint with 1.25% onRS of 1,5,7-triazabicyclo(4.4.0)dec-5-ene coming from the grind vehicle.Fifteen percent by weight of the paint was removed by ultrafiltrationand replaced by deionized water.

Example 18 (a) A Paint

# Material Parts 1 Cationic resin Example 8 148.28 2 Butyl carbitolFormal¹ 6 3 Cationic resin, Example 7 53.35 4 Example 3 Cationic resin(at 38.1% NV) 1086.56 5 Ethylene Glycol hexyl ether 13.5 6 Example 12,Pigment Paste 168.03 7 Deionized water 1092.31 ¹Available as MAZON 1651from BASF Corporation

Materials 1-5 are added sequentially under agitation and stirred untiluniform to create the resin blend. Material 6 was added and the paintwas allowed to stir until uniform. Material 7 was added, and the paintwas allowed to stir overnight. This results in a paint with no catalyst.

Example 19 (a) A Cationic Resin

A EPON 880¹ 464.01 Bisphenol A 153.61 Ethylene glycol mono-2-ethyl hexylether 12.00 B Ethyltriphenyl phosphonium iodide 0.72 C Ethylene glycolmono-2-ethyl hexyl ether 56.76 D Crosslinker² 495.07 E1,5,7-triazabicyclo(4.4.0)dec-5-ene 21.21 F sulfamic acid 27.55 H2O 438G H2O 891.97 H H2O 131 ¹Epoxy resin available from Hexion SpecialtyChemicals ²Crosslinker prepared from the reaction of Hexamethylenetriamine and propylene carbonate (detailed below).

Procedure: All weights are in grams. Items A and B are charged to a 4neck round bottom flask, fit with a stirrer, temperature measuringprobe, N₂ blanket and heated to 125° C. The mixture exotherms. Begin 1hour hold at 160° C. The peak exotherm was 171° C. and the temperatureallowed to drop to 160° C. After 1 hour, charge C was added. Charge Dthen was added and the mixture was held at 115° C. for 30 minutes.Charge E then was added and the mixture held for an additional 30minutes. 1260g of the reaction mixture was poured into a solution ofitem F with good stirring. The resulting dispersion was mixed for thirtyminutes and then charge G was added with stirring over about 30 minutesand mixed well. Charge H was added and mixed well. Water and solventthen were distilled off under vacuum at 60-65° C. The resulting aqueousdispersion had a solids content 39.19%.

(b) Preparation of the crosslinker

1 Bishexamethylene triamine 135.4 2 Propylene carbonate 112.3 3 Ethyleneglycol mono-2-ethyl hexyl ether 61.93

Charge 1 to a reactor. Add 2 dropwise over two hours. The reactionexotherms. Adjust the addition rate such that the temperature does notexceed 70° C. The reaction was then diluted with ethylene glycolmono-2-ethyl hexyl ether.

Example 20 (a) A Paint

# Material Parts 1 Cationic resin Example 19 1454 2 Deionized water 2346

Materials 1 and 2 are added sequentially under agitation and stirreduntil uniform to create the resin blend. This results in a paint with1.99% on RS of 1,5,7-triazabicyclo(4.4.0)dec-5-ene.

Example 21 (a) Cure Results Set 2

The electrodepositable coating compositions of examples 13, 14, 17, 18,20 were electrodeposited onto phosphated steel under conditionssufficient to provide an electrodeposited film thickness of about 24micrometers using procedures known to those skilled in the art. Thepanels were then cured in an electric oven at the temperatures and timesindicated. The panels were tested for cure by acetone double rubs usingASTM D5402-6 Method A with the following exceptions: Acetone was usedrather than MIBK, no water cleaning of panel, 100 double rubs are doneusing a cheese cloth, and the rating scale is as listed below.

1 through to substrate in <50 2 Through in 50-100 rubs 3 Very severelymarred. Scratches to metal easily 4 Severely marred only over arearubbed. Can Scratch to metal 5 Marred over rub area, can scratch throughto metal 6 Marred uniformly in center of rub area, difficult, butpossible to scratch to metal 7 Non uniform marring over rub area, cannot scratch to metal 8 Scratching, very little marring of rub area, cannot scratch to metal 9 Slight scratching of rub area, can not scratch tometal 10 No visible damage

% DBTO % BCG* Acetone double Paint on Resin Additive on Rub ExampleSolids Resin Solids Temp Time Rating Rubs Example 0 1.28 138 C. 30′ 1 513 149 C. 30′ 8 100 160 C. 30′ 8 100 171 C. 30′ 8 100 Example 0 1.25 138C. 30′ Not run Not run 17 149 C. 30′ Not run Not run 160 C. 30′ 2 81 171C. 30′ 6 100 Example 0 1.99 138 C. 25′ Not run Not run 20 149 C. 25′ 7/8100 160 C. 25′ 8 100 171 C. 25′ 8/9 100 Example 0 0 138 C. 30′ Not runNot run 18 149 C. 30′ 1 2 160 C. 30′ 1 3 171 C. 30′ 1 5 Example 1.3 0138 C. 30′ Not run Not run 14 149 C. 30′ 1 12 160 C. 30′ 7 100 171 C.30′ 8 100 *1,5,7-triazabicyclo(4.4.0)dec-5-ene

Example 22 (a) A Catalyst Paste

# Material gms 1 Example 11, Cationic Resin 515.70 2 Bismuth III Oxide241 3 Sulfamic Acid 100 4 Deionized Water 315 5 Deionized Water 50

Materials 1 and 2 were added to 2 liter steel beaker and mixed underhigh shear cowles blade agitation. Materials 3 and 4 were premixed andadded slowly to the bismuth resin paste and the resulting mixture wasstirred under high shear cowles agitation for an additional 30 minutes.Material 5 was added, and the paste was media milled 3 hours in aChicago Boiler Red Head Mill equipped with a water cooling jacket using2 mm round zircoa media.

Example 23 (a) A Grind Vehicle

This example describes the preparation of a quaternary ammonium saltcontaining pigment-grinding resin. Example 23-1 describes thepreparation of an amine-acid salt quaternizing agent and Example 23-2describes the preparation of an epoxy group-containing polymer that wassubsequently quaternized with the amine-acid salt of Example 23-1.

23-1

The amine-acid salt quaternizing agent was prepared using the followingprocedure:

# Material Parts 1 Dimethyl ethanolamine 445 2 PAPI 290¹ 660 4 88%lactic acid aqueous 512 5 Deionized water 2136.11 ¹Polymericdiisocyanate commercially available from Dow Chemical Co. 2. Availableas MAZON 1651 from BASF Corporation

To a suitably equipped 5 liter flask material 1 was charged. Material 2was then charged under mild agitation over a 1.5 hour period, followedby a rinse of material 3. During this addition, the reaction mixture wasallowed to exotherm to a temperature of about 89° C. and held at thattemperature for about 1 hour until complete reaction of the isocyanateas determined by infrared spectroscopy. At that time, material 4 wasadded over a 25 minute period, followed material 5. The reactiontemperature was held at about 80° C. for about 6 hours until a stalledacid value of 70.6 was obtained.

23-2

The quaternary ammonium salt group-containing polymer was prepared usingthe following procedure.

# Material Parts 1 Bisphenol A Diglycidyl ether¹ 528.8 2 Bisphenol A224.9 3 Butyl Carbitol Formal² 83.7 4 ethyltriphenylphosphonium iodide0.5 5 Butyl Carbitol Formal² 164.9 6 amine-acid quaternizing agent 23-1418.4 7 Deionized water 1428.1 8 Butyl Carbitol Formal² 334.7¹Diglycidyl ether of Bisphenol A commercially available from ResolutionChemical Co as EPON 828. ²Available as MAZON 1651 from BASF Corporation

Material 1 was charged to a suitably equipped 5 liter flask were added,under mild agitation. Material 2 was then added followed by material 3and material 4. The reaction mixture was heated to about 140° C.,allowed to exotherm to about 180° C., then cooled to about 160° C. andheld at that temperature for about 1 hour. At that time the polymericproduct had an epoxy equivalent weight of 982.9. The reaction mixturewas then cooled to a temperature of about 130° C. at which time material5 was added and the temperature lowered to about 95°-100° C., followedby the addition of material 6, the amine-acid quaternizing agent of 23-1over a period of 15 minutes, and subsequently followed by the additionof about 1428.1 parts by weight of deionized water. The reactiontemperature was held at about 80° C. for approximately 6 hours until theacid number of the reaction product fell below 1.0. The resultantquaternary ammonium salt group-containing pigment grinding resin wasfurther reduced with about 334.7 parts by weight of the solvent of ButylCarbitol Formal.

Example 24 (a) A Grind Vehicle

# Material gm 1 EPON 828¹ 533.2 2 nonyl phenol 19.1 3 bisphenol A 198.34 ethyltriphenyl phosphonium iodide 0.7 5 butoxy propanol 99.3 6 butoxypropanol 93.9 7 methoxy propanol 50.3 8 Thiodiethanol 121.3 9 butoxypropanol 6.9 10 deionized water 32.1 11 dimethylol propionic acid 133.112 Deionized water 1100 13 Deionized water 790 ¹Diglycidyl ether ofBisphenol A commercially available from Resolution Chemical Co as EPON828.

Charge materials 1 through 5 to a suitably equipped flask and heat to125° C. The mixture was allowed to exotherm to 175° C. and then held at160-165° C. for 1 hr. After the 1 hr hold add materials 6-7. Cool to 80°C. and add materials 8-11. Hold at 78° C. until the measured acid valuewas less than 2. When the acid value was OK, pour 1288.2 g of the resininto 1100 g of deionized water (material 12) with stirring. Mix for 30minutes then add material 13 and mix well. 30% of the coatingcomposition was removed by ultrafiltration and replaced with deionizedwater.

Example 25 (a) A Pigment Paste

# Material gm 1 Cationic Resin example 23 418.6 2 Cationic Resin example24 2267.2 3 SURFYNOL GA¹ 84.5 4 Ethylene glycol hexyl ether 39 5 TiO₂ ²2780 6 POLSPERSE 10³ 208 7 PRINTEX 200⁴ 52 8 Yttrium Oxide 84.5 9Deionized water 300 10 FA810⁵ 4698.9 ¹A Surfactant available from AirProducts Inc. ²CR800E available from Kerr McGee ³A Kaolin clay availablefrom IMERYS Inc. ⁴A carbon black available from Degussa Inc. ⁵A cationicsilica paste, 10.52% parts silica, manufactured by PPG Industries.

Materials 1-8 were preblended in a flat bottom plastic container.Material 9 was added to the mixture to reduce viscosity. The paste wasthen milled on a PREMIER mill until a Hegman reading of >7 was observed.Material 10 was then added to the paste and the paste was milled for anadditional hour.

Example 26 (a) A Paint

# Material Parts 1 W7718. Cationic resin Blend¹ 100 2 Pigment pasteExample 25 14.89 3 Catalysts paste Example 22 2.45 4 Deionized water84.24 ¹A cationic, automotive electrodepositable resin blendcommercially available from PPG Industries

Materials 1 through 4 are added sequentially under agitation and allowedto stir 24 hours. This paint was 21.5% solids, 1.2% bismuth on totalresin solids from all paint components. This paint was made to a scaleof 12000 grams. 30% of the coating composition was removed byultrafiltration and replaced with deionized water.

Example 27 (a) An Additive Dispersion

# Material gm 1 Sulfamic Acid 8.05 2 Deionized water 60 3 Example 431.95

Materials 1 and 2 were blended until uniform. Material 3 was then addedunder agitation forming a dispersion.

Example 28 (a) A Paint

# Material gm 1 Electrodepositable coating Example 26 2865.67 2 Additivedispersion Example 27 34.7 3 Deionized water 99.63

Material 2 and 3 were preblended and added to a portion of paint 1(material 1) under agitation. This paint was 21.0% solids, 1.17%bismuth, and 2% of Additive of example 4 on total resin solids from allpaint components. 30% of the coating composition was removed byultrafiltration and replaced with deionized water.

Example 29 (a) A Cationic Resin

# Material gm 1 EPON 828¹ 430.27 2 Bisphenol A 185.8 3 MACOL 98 A MOD 1²87.5 4 Methylisobutyl ketone (mibk) 21.76 5 Ethyltriphenyl phosphoniumiodide 0.42 6 MACOL 98 A MOD 1² 65.54 7 Methylisobutyl ketone (mibk)12.13 8 Ketimine³ 53.37 9 N-methyl ethanolamine 28.06 101,5,7-triazabicyclo(4.4.0)dec-5-ene 10.73 11 Crosslinker⁴ 434.44 12sulfamic acid 43.46 13 H2O 1080.18 14 H2O 1521.15 ¹Epoxy resin availablefrom Hexion Specialty Chemicals. ²Bisphenol ethylene oxide adductavailable from BASF Corporation. ³MIBK diketimine of diethylene triamineat 72.7% in MIBK. ⁴MDI blocked urethane crosslinker, the reactionproduct of 10 equivalents of Lupranate M70L (a polymeric MDI), 2equivalents of ethanol and 8 equivalents of methanol. Used at 80% solidsin MIBK.

Procedure: All weights are in grams. Items 1, 2, 3, 4 and 5 are chargedto a 4 neck round bottom flask, fit with a stirrer, temperaturemeasuring probe, N₂ blanket and heated to 130° C. The mixture exotherms,but was not allowed to exceed 145° C. The temperature was held at 145°C. and for 2 hours. Charges 6 and 7 were then added. Reaction wasallowed to proceed until an epoxy equivalent weight of 1167 wasobserved. Charges 8, 9 and 10 were added and the mixture was held at122° C. for two hours. The heat was turned off, and material 11 wasadded and the mixture was stirred for 10 minutes. The reaction mixturewas poured into a solution of items 12 and 13 with good stirring. After30 minutes, material 14 was added slowly over 30 minutes. About 700 g ofwater and solvent are distilled off under vacuum at 60-65° C., andreplenished with deionized water The resulting aqueous dispersion had asolids content of 37.9%.

Example 30 (a) A Cationic Resin

1 MAZEEN 355 70¹ 1423.49 2 acetic acid 15.12 3 Dibutyltindilaurate 1.524 Toluene diisocyanate 80/20 200.50 5 sulfamic acid 79.73 6 deionizedH2O 1623.68 7 deionized H2O 766.89 ¹Amine functional diol of amineequivalent weight 1131 available from BASF Corporation.

Items 1 and 2 are charged to a 4 neck round bottom flask, fit with astirrer, temperature measuring probe and N₂ blanket and mixed for 10minutes. Item 3 was added and then item 4 was charged over about 1 hourallowing the reaction mixture to exotherm to a maximum temperature of100° C. The mixture was then held at 100° C. until the infrared spectrumindicates the absence of isocyanate (approximately 1 hour). 1395 g ofthe reaction mixture was poured into a mixture of items 5 and 6 andmixed for 1 hour. Item 7 was then added over about 1 hour and mixed forabout 1 hour. The resulting aqueous solution had a solids content ofabout 36%.

Example 31 (a) A Paint

# Material Parts 1 Cationic resin Example 29 1371.5 2 plasticizer¹ 189.83 Butyl carbitol Formal² 39.5 4 Propylene glycol phenyl ether 3.5 5Cationic Resin Example 30 36.6 6 Cationic Resin Example 7 73.3 7 NoromoxC5³ 3.3 8 Surfactant Blend⁴ 5.2 9 Paste⁵ 212.1 10 Deionized water 1865.3¹A plasticizer available from PPG industries. ²Available as MAZON 1651from BASF Corporation. ³A surfactant available from CECA S.A. ⁴A blendof solvents and surfactants consisting of 31.26 parts ethylene glycolbutyl ether, 31.26 parts SURFYNOL 104 ™ available from Air Product Inc,32.46 parts Noramox C5 available from CECA S.A., 5 parts acetic acid.⁵Similar paste to Example 12 with material 1 replace by the grindvehicle of example 24 on a resin solids basis. Used at 57% total solids.

Materials 1-8 are added sequentially under agitation and stirred untiluniform to create the resin blend. Material 9 was added and the paintwas allowed to stir until uniform, minimum 30 minutes. Material 10 wasadded, and the paint was allowed to stir until uniform, minimum 30minutes.

Example 32 (a) A Paint

# Material Parts 1 Paint from Example 31 3200 2 Ethylene Glycol ButylEther 9.5 3 Ethylene Glycol Hexyl Ether 9.5 4 Zinc Oxide (ZnO) 1.73

Materials 1 through 4 were added sequentially to a 4 liter containerunder agitation with 10 minutes stirring between adds. This results inan electrodepositable paint with 0.7%1,5,7-triazabicyclo(4.4.0)dec-5-ene and 0.2% zinc metal on resin solids.

Example 33 (a) Cure Results Set 3

For of examples 24, 26, 31, and 32, each electrodepositable coatingcompositions was then electrodeposited onto phosphated cold rolled steelunder conditions sufficient to provide an electrodeposited filmthickness of about 24 micrometers. The panels were then cured for 20minutes at 175 C and tested for cure by acetone double rubs using ASTMD5402-6 Method A with the following exceptions: Acetone was used ratherthan MIBK, no water cleaning of panel, 100 double rubs are done using acheese cloth, and the rating scale was as listed below.

1 through to substrate in <50 2 Through in 50-100 rubs 3 Very severelymarred. Scratches to metal easily 4 Severely marred only over arearubbed. Can Scratch to metal 5 Marred over rub area, can scratch throughto metal 6 Marred uniformly in center of rub area, difficult, butpossible to scratch to metal 7 Non uniform marring over rub area, cannot scratch to metal 8 Scratching, very little marring of rub area, cannot scratch to metal 9 Slight scratching of rub area, can not scratch tometal 10 No visible damage

% BCG % Bi Additive % Zn on on ARD ADR Paint Resin Resin Resin RatingRubs Example Description Solids Solids Solids 20′ 175 C. 20′ 175 C.Example 26 Control 1.2% Bi 0 1.2 0 2 (92)* Example 28 1.2% Bi + 2% BCG 01.17 2 7 100  2EHGE Example 31 BCG low level 0 0 .7 1 (<45)*  Example 32BCG low level + Zn .2 0 .7 2 (87)* BCG Additive =1,5,7-triazabicyclo(4.4.0)dec-5-ene + 2 ethyl hexyl glycidyl ether fromExample 4 BCG = 1,5,7-triazabicyclo(4.4.0)dec-5-ene ADR = Acetone DoubleRubs *Rubbed through to metal in reported rubs

1. A method for coating a substrate comprising: (a) introducing thesubstrate into an electrodeposition bath having an electrodepositablecoating composition, wherein said electrodepositable coating compositioncomprises a cyclic guanidine; and (b) electrodepositing saidelectrodepositable coating composition onto a surface of said substrateto form a coated layer on said surface.
 2. The method according to claim1 further comprising: (c) curing said coated layer to form a cured filmlayer on said surface of said substrate.
 3. The method according toclaim 1, wherein said electrodepositable coating composition comprises areaction product of a polymer and said cyclic guanidine.
 4. The methodaccording to claim 3, wherein said polymer comprises an epoxy functionalpolymer.
 5. The method according to claim 3, wherein saidelectrodepositable coating composition further comprises an additionalcomponent that is reactive with said functional group wherein saidadditional component comprises a polyamine, a primary amine, a secondaryamine, a tertiary amine, a sulfide, or combinations thereof.
 6. Themethod according to claim 5, wherein said additional component comprisesa reaction product of said polyamine and a carbonate.
 7. The methodaccording to claim 6, wherein said polyamine comprises at least oneprimary amine and at least one secondary amine.
 8. The method accordingto claim 7, wherein at least a portion of the primary amine of saidpolyamine is reacted with said carbonate to form a carbamate.
 9. Themethod according to claim 8, wherein the carbonate is a cycliccarbonate.
 10. The method according to claim 3, wherein saidelectrodepositable coating composition further comprises a curing agent.11. The method according to claim 10, wherein said curing agentcomprises a urethane, an isocyanate, an ester, or combinations thereof.12. The method according to claim 11, wherein the urethane curing agentcomprises a reaction product of a polyamine and a carbonate.
 13. Themethod according to claim 12, wherein said carbonate comprises a cycliccarbonate.
 14. The method according to claim 10, wherein said curingagent comprises a reaction product of said cyclic guanidine and anisocyanate.
 15. The method according to claim 1 wherein said cyclicguanidine comprises structure (II) and/or structure (III):

wherein each of R1, R2, R3, R4, R5, R6, R7 comprise hydrogen,(cyclo)alkyl, aryl, aromatic, organometallic, a polymeric structure, ortogether can form a cycloalkyl, aryl, or an aromatic structure, andwherein R1, R2, R3, R4, R5, R6, and R7 can be the same or different, andwherein n≧1.
 16. The method according to claim 1, wherein said cyclicguanidine is polycyclic and comprises structure (IV) and/or structure(V):

wherein each of R1, R2, R3, R4, R5, R6, R7, R8, or R9 compriseshydrogen, (cyclo)alkyl, aryl, aromatic, organometallic, a polymericstructure, or together can form a cycloalkyl, aryl, or an aromaticstructure, and wherein R1, R2, R3, R4, R5, R6, R7, R8, and R9 can be thesame or different, and wherein n and m are both ≧1, and wherein n and mmay be the same or different.
 17. The method according to claim 1,wherein said cyclic guanidine comprises1,5,7-triazabicyclo[4.4.0]dec-5-ene.
 18. The method according to claim1, wherein said electrodepositable coating composition further comprisesa metal, a metal oxide, a metal salt, an alkyl metal, an alkyl metaloxide, an alkyl metal salt, or combinations thereof.
 19. The methodaccording to claim 1, wherein said cyclic guanidine comprises 0.01% to7% by weight based on weight of the total resin solids of saidelectrodepositable coating composition.
 20. The method according toclaim 1, wherein said electrodepositable coating composition furthercomprises a crater control additive, and wherein said crater controladditive comprises said cyclic guanidine.
 21. The method according toclaim 1, wherein said electrodepositable coating composition furthercomprises a microgel, and wherein said microgel comprises said cyclicguanidine.
 22. The method according to claim 1, wherein saidelectrodepositable coating composition comprises a reaction product ofsaid cyclic guanidine and a monofunctional compound.
 23. The methodaccording to claim 22, wherein said monofunctional compound comprises amono-glycidyl compound.
 24. A coating composition used for coating asubstrate via an electrodeposition process, the coating compositioncomprising a cationic reaction product of reactants comprising: amonofunctional compound; and cyclic guanidine.
 25. The coatingcomposition according to claim 24, wherein said monofunctional compoundcomprises a mono-glycidyl compound.
 26. The coating compositionaccording to claim 24, wherein said monofunctional compound comprises afunctional group that reacts with cyclic guanidine.
 27. The coatingcomposition according to claim 24 wherein said cyclic guanidinecomprises structure (II) and/or structure (III):

wherein each of R1, R2, R3, R4, R5, R6, R7 comprise hydrogen,(cyclo)alkyl, aryl, aromatic, organometallic, a polymeric structure, ortogether can form a cycloalkyl, aryl, or an aromatic structure, andwherein R1, R2, R3, R4, R5, R6, and R7 can be the same or different, andwherein n≧1.
 28. The coating composition according to claim 27, whereinn≧2.
 29. The coating composition according to claim 27, wherein n≧3. 30.The coating composition according to claim 24, wherein said cyclicguanidine is polycyclic and comprises structure (IV) and/or structure(V):

wherein each of R1, R2, R3, R4, R5, R6, R7, R8, or R9 compriseshydrogen, (cyclo)alkyl, aryl, aromatic, organometallic, a polymericstructure, or together can form a cycloalkyl, aryl, or an aromaticstructure, and wherein R1, R2, R3, R4, R5, R6, R7, R8, and R9 can be thesame or different, and wherein n and m are both ≧1, and wherein n and mmay be the same or different.
 31. The coating composition according toclaim 30, wherein n and m=1.
 32. The coating composition according toclaim 30, wherein n and m=2.
 33. The coating composition according toclaim 30, wherein n=1 and m=2.
 34. The coating composition according toclaim 24, wherein said cyclic guanidine comprises1,5,7-triazabicyclo[4.4.0]dec-5-ene.